Color photographic material comprising nondiffusing coupler and dir hydroquinone

ABSTRACT

A photographic material comprising a support coated with (1) a first light-sensitive layer containing a silver halide emulsion preferably a coarse grain emulsion either alone or with a nondiffusing color-forming coupler that forms a dye upon color development and (2) a second light-sensitive layer containing a silver halide emulsion preferably a finer grain rapidly developing silver halide and a nondiffusing coupler that forms a dye, and a nondiffusible development inhibitor-releasing hydroquinone compound that releases a diffusible development inhibitor upon color development by a primary aromatic amine color developing agent, is used advantageously to record a first light image in the first layer and a second light image in the second layer and produce upon color development an image reproduction of the second light image in the second layer and produce a visible image reproduction of the first light image in the first layer, said visible image reproduction having reduced contrast in areas that correspond to the image reproduction formed in the said second layer.

United States Patent [72] Inventor Charles R. Barr Rochester, N.Y. [2!] App]. No. 717,923

[22] Filed [45] Patented [73] Assignec [54] (IOLOR IHOTOGRAPHIC MATERIAL (10M PRlSlNG NONDIFFUSING COUPLER AND DIR HYDROQUINONE 20 Claims, N0 Drawings [52] US. Cl ..96/3,96/68, 96/74, 96/29 [51] Int. Cl G03c 1/76 [50] Field of Search 96/74,100, 68, 3, 29

[56] References Cited UNITED STATES PATENTS 3,140,179 7/1964 Russell 96/68 3,148,062 9/1964 Whitmore et al. 96/100 X 3,227,551 l/1966 Barret al. 96/74 Primary Examiner-Norn1an G. Torchin Assistant Examinerlohn L. Goodrow Al!orneys-William H. J. Kline, James R. Frederick and Ray Carter Livermore ABSTRACT: A photographic material comprising a support coated with (l) a first light-sensitive layer containing a silver halide emulsion preferably a coarse grain emulsion either alone or with a nondiffusing color-forming coupler that forms a dye upon color development and (2) a second light-sensitive layer containing a silver halide emulsion preferably a finer grain rapidly developing silver halide and a nondiffusing coupler that forms a dye, and a nondiffusible development inhibitor-releasing hydroquinone compound that releases a diffusible development inhibitor upon color development by a primary aromatic amine color developing agent, is used advantageously to record a first light image in the first layer and a second light image in the second layer and produce upon color development an image reproduction of the second light image in the second layer and produce a visible image reproduction of the first light image in the first layer, said visible image reproduction having reduced contrast in areas that correspond to the image reproduction formed in the said second layer.

COLOR PHOTOGRAPI'IIC MATERIAL COMPRISING NONDIFFUSING COUPLER AND DIR IIYDROQUINONE This invention is related to photography including sensitive photographic materials and processes for recording a plurality of separate images and reproducing them as vividly different image reproductions.

ln color photography it is known to use color photographic materials containing differently sensitized silver halide emulsion layers that contain incorporated color-forming couplers which upon color development form differently colored dye images that combine to form the resulting color reproduction. Usually the red-sensitized silver halide emulsion layer contains a phenolic or naphtholic dye-forming coupler, the green-sensitized silver halide emulsion layer contains a magenta-forming pyrazolone coupler and the blue-sensitive silver halide emulsion layer contains an open-chain yellow dye-forming coupler. In these photographic elements great care is exercised in adjusting the speeds and sensitometric characteristics of the three differently sensitized emulsion layers so that the resulting dye images will have ideally the same relationship of dye density to exposure. This is necessary so that a gray scale can be reproduced and also so that a colored image will reproduce with the same color regardless of the exposure given providing it is within the sensitivity range of the photographic film. It is also known in color photography to use twoequivalent couplers which require only one-half the amount of silver halide development to produce a given amount of dye that is required by four-equivalent couplers.

The use of development inhibitor-releasing hydroquinone compounds in direct positive color reproduction process is described in Barr US. Pat. No. 3,364,022, issued Jan. 16, 1968.

In photographic recording systems, it is often desired to record two separate images and be able to study them in superposed relationship. When one of the two images is made up of small and especially minute image areas, such as fine lines, small dots, etc., they may be difficult to distinguish from the second image. It is known to reproduce two such images in dif ferent colors, however, even then the fine line or dots may be very difficult to distinguish in areas where a second image reproduction underlies them because of the degradation or darkening of the color of the fine line or dot by the color of the underlying image.

For aerial reconnaissance, it is desired to record a light image of a map emitted from a phosphor-coated radar screen from side-looking radar (referred to hereinafter as SLR) and to simultaneously record a second light image emitted from a phosphor-coated radar screen showing moving target information (referred to hereinafter as MTI) from the same area represented or shown by the map. The radar signals received by the radar scope providing MTI are electronically filtered so that the radar scope shows only images of moving objects. In

order for the processed pictures to serve the purpose for which they are intended, they must be available quickly and be combined in such a way that the images are properly registered. A photographic material and process is desired for simultaneous recording of the SLR and MTI images and then processing them so that even when the MTI image reproductions are' very small, they are vividly distinct from the SLR map image reproduction.

It is an object of my invention to provide a novel light-sensitive photographic material and process capable of recording a plurality of images and reproducing them so that even very minute details in the reproduction of the images are vividly discernible. Another object of my invention is to provide a novel lightsensitive photographic material and process for recordingand reproducing images of very small moving targets so they are very readily discernible against the underlying image of a sidelooking radar map.

Another object of my invention is to provide a novel multilayer light-sensitive photographic material and process for recording and reproducting images of at least two colors so that the color development of one image in one layer reduces the contrast of an image in a second layer and at the same time increases the sharpness of the edges of the images.

These and still other objects will be apparent from consideration of the following specification and claims.

These and still other objects are accomplished according to my invention by the preparation and use of my novel photographic recording materials. In the simplest form, one embodiment of my photographic recording material comprises a support coated with a first light-sensitive hydrophilic colloid layer containing a silver halide emulsion, preferably a coarse grain emulsion sensitive to at least one region of the actinic spectrum (i.e., light of from about So to about l,200p. which silver halide emulsions will record) either alone or with a colorforming coupler (preferably a nondiffusing coupler) that reacts with an oxidized primary aromatic amine color developer and forms a dye image, and a second light-sensitive hydrophilic colloid layer containing a silver halide emulsion (preferably a finer grained rapidly developing silver halide emulsion) sensitive to at least one region of the actinic spectrum that is different from the region(s) of the actinic spectrum to which the said silver halide emulsion in the first lightsensitive layer is sensitive and contiguous to silver halide grains of the emulsion in thesecond light-sensitive layer, a coupler that reacts with oxidized primary aromatic amine color developer to form a dye image which advantageously has a different color than a dye image formed in the first lightsensitive layer and a nondiffusing development inhibitorreleasing (DIR) hydroquinone compound that cross-oxidizes with an oxidized primary aromatic amine color-developing agent to release a diffusible development inhibitor. During color development of a preferred material of my invention, the finer grained rapidly developing silver halide emulsion is substantially completely developed and the imagewise pattern of development inhibiting agent has diffused into the coarser grained silver halide emulsion layer before it starts to develop so the development-inhibiting agent very substantially, if not completely, inhibits development of the silver halide emulsion in the first light-sensitive layer directly under (or over) the silver and dye image formed in the second light-sensitive layer. Although the development inhibitor substantially inhibits development of the silver halide emulsion in areas of the first light-sensitive layer under (or over) the silver and dye image formed in the second light-sensitive layer, the development inhibitor has substantially no inhibiting effect on the development of the silver halide in the second light-sensitive layer. This insures a good silver and dye image in the second lightsensitive layer with essentially no image, if any, being formed in the first light-sensitive layer directly under (or over) it so that the image in the second light-sensitive layer is very readily discernible from images in the first light-sensitive layer. This embodiment of my photographic recording material is used to advantage to record two separate differently colored images by exposure through one side, e.g., to record an image of an SLR map which is optically combined and registered with the radar information showing MTI so that the film is exposed in a single step with the SLR map image recorded in the first lightsensitive layer and the radar information showing MTI recorded in the second light-sensitive layer.

In the simplest form of another embodiment of my photographic recording material, the first light-sensitive hydrophilic colloid layer described previously, is separated from the second light-sensitive hydrophilic colloid layer described previously by a hydrophilic colloid layer containing a bleachable light-absorbing filter that will absorb the exposing image light. These layers are coated on a transparent support and the exposure of the one image, e.g., SLR map image is made through the transparent support while exposure of the second image, e.g., the radar information showing MTI is made directly onto the top layer in such a way that the two images when developed will be in register. Since a light-absorbing filter layer is used to confine the exposure of each of the two light-sensitive layers to the respective light image each is sup posed to record in this embodiment, the two emulsions need not be spectrally sensitized or they can be advantageously spectrally sensitized in any way desired including identical spectral sensitization.

in another embodiment of my invention a support is coated with (l) a first hydrophilic colloid layer containing a first finer grained rapidly developing silver halide emulsion sensitive to at least one region of the actinic spectrum and contiguous to the silver halide grains in this emulsion a first colorless nondiffusible coupler that reacts with oxidized primary aromatic amine color-developing agent to form a first nondiffusible dye and contiguous to this same emulsion a DIR hydroquinone compound that cross-oxidizes with an oxidized primary aromatic amine color-developing agent and then releases a diffusible development inhibitor, (2) a second hydrophilic colloid layer containing a coarse grain slower developing emulsion that is sensitive to at least one region of the actinic spectrum that is different than the emulsion in (l) and contiguous to the silver halide grains in the said coarse grain emulsion, a colorless nondiffusing coupler which reacts with oxidized primary aromatic amine color developer to form a second nondiffusing dye having a color that is different from that formed by reaction of the said coupler in (l), and (3) a hydrophilic colloid layer containing a second finer grained rapidly developing silver halide emulsion sensitive to at least one region of the actinic spectrum that is different from the regions that the silver halide emulsions in (l) and (2) are sensitive to, and contiguous to the silver halide grains in the said second finer grain emulsion, a second colorless nondiffusing coupler that reacts with oxidized primary aromatic amine colordeveloping agent to form a third nondiffusing dye having a color that is different from the dyes formed by the reaction of the said couplers in (l) and in (2), and contiguous to the silver halide in this second finer grain emulsion a DIR hydroquinone compound which cross-oxidizes with oxidized primary aromatic amine color-developing agent and releases a diffusible development inhibitor. Upon development with a primary aromatic amine color developer, exposed silver halide in the first and third layers is very rapidly developed to the respective silver and dye images with the release of development inhibitor in each of these layers which diffuses into the said second layer and substantially inhibits the development of any latent image in that layer that corresponds to a dye image developed in either or both the first and third layers.

In another embodiment, variations of the above embodiments are used in which two or more of the sets of light sensitive layers described above are coated on a single support. The different silver halide emulsions in such an element are advantageously spectrally sensitized so that each one responds to an appropriate range of wavelengths in the actinic spectrum v that is different from those to which the others respond.

Similarly the couplers are advantageously chosen so that they produce upon color development differently colored dyes. Preferably dyes are chosen which are as different as possible, however, when more than three or four different dye images are needed the differences will be smaller and it is advantageous to select dyes which have sharply cutting absorption curves with A max values that are distinctly different from those of the other dyes used in the element. Where desired in such elements to prevent development inhibitor released in one set of the light-sensitive layers from affecting development in a layer of another set of light-sensitive layers, it is advantageous to coat an interlayer containing colloidal silver, silver halide or other material that will prevent diffusion of the development inhibitor.

In another embodiment of my invention a support is coated with a first light-sensitive hydrophilic colloid layer containing a coarse grain silver halide emulsion sensitive to one region of the actinic spectrum with or without a colorless nondiffusing coupler that reacts with oxidized primary aromatic amine color developer to produce a first dye image and a second light-sensitive hydrophilic colloid layer containing a dispersion of a plurality of differently sensitized packets each containing a fine grain rapidly developing silver halide emulsion and contiguous to the silver halide grains in the packet an uncolored nondiffusing coupler which reacts with oxidized primary aromatic amine color-developing agent to form a nondiffusing dye. Packets sensitive to one region of the actinic spectrum are designed to produce a dye image that has a different color than the dye images produced by packets sensitized to other regions.

It is advantageous but not necessary to include between light-sensitive layers a non-light-sensitive hydrophilic colloid layer containing a scavenger to prevent oxidized colordeveloping agent from wandering from one light-sensitive layer to the next.

My photographic materials are developed by contacting the photographic element with an aqueous alkaline color developer solution containing a primary aromatic amine color-developing agent which upon penetrating the hydrophilic colloid layers rapidly produces a silver and a dye image of the latent image in the finer grain, rapidly developing silver halide emulsion and liberates the development-inhibiting agent in an imagewise pattern corresponding to the silver and dye image formed. The imagewise pattern of developmentinhibiting agent and color developer diffuse into the next emulsion layer to inhibit development of the latent image in the coarse grain silver halide emulsion in areas corresponding to the developed image in the other layer, while the colordeveloping agent develops the other parts of the latent image into a visible image comprising a silver image and a dye image (when a color-forming coupler has been incorporated in this layer). The development-inhibiting effect in the coarse grain slower developing silver halide emulsion layer often extends to an area slightly larger than the silver and dye image in the finer grain rapidly developing layer so this image is encircled by a narrow, clear area in which there is no silver or dye image in the coarse grain image layer. This effect is very advantageous since it still further sets out one image against the other image. In my photographic materials which contain couplers in all the light-sensitive layers, the silver images may be removed from the film by treatment with an oxidizing agent such as a solution of potassium ferricyanide or cupric chloride followed by hypo solution which removes both oxidized silver and the undeveloped silver halide. This treatment leaves only the dye images in the film, a bright dye image of one color in the top layer superposed upon a differently colored image reproduced in the bottom layer with substantially no degradation of the brightly colored image in the top layer by an underlying image in the bottom layer. As was mentioned previously, the top layer images are often encircled with a clear area in the bottom layer even in areas where a latent image had been previously produced in that layer.

For the sake of simpler and more rapid processing of the film, it may be advantageous to omit the removal of the silver images and the undeveloped silver halide by the substitution of a stabilizing solution, such as thiourea, in place of bleaching and fixing as was described above. No bleaching step could be used, of course, for the processing of my photographic elements which do not use a color-forming coupler in both layers. This procedure will leave a silver image in one layer and a silver and dye image in the other layer. Consequently, it is desirable to use in the top layer a fine grain emulsion that will produce a fine grain silver image that will be as transparent as possible.

In theembodiments of my invention couplers forming diffusible dyes are advantageously used in the light-sensitive layers or packets, or alternatively mixtures of couplers that form nondiffusible dyes together with couplers that form diffusible dyes are advantageously used in one or all of the lightsensitive layers or packets. The couplers in such a mixture can form dyes that have the same or different spectral absorptions providing differently colored nondiffusible dyes are formed'in the different light-sensitive layers or packets and differently colored diffusible dyes are formed in the different light-sensitive layers or packets. The diffusible dye images are transferred to a separate mordanted reception sheet by contacting during development or a reception sheet that is an integral part of the element with a strippable layer coated between one of the image-forming layers and the mordant layer of the reception sheet. After development, the reception sheet is separated from the image-forming layers carrying the composite of the diffusible dye images. It is advantageous to remove residual developer solution from the image-bearing reception sheet. Where nondiffusible dye images are formed in the image-forming layers, these are washed, then fixed, or bleached and fixed, or blixed, then washed as described previously.

In another embodiment of my invention, my DlR hydroquinone compounds are incorporated advantageously in one or more layers of multilayer materials for color photography having differently sensitized silver halide emulsions each incorporating an appropriate nondiffusing dye-forming coupler that forms a nondiffusible dye image that is complementary in color to the colbr of light the emulsion is sensitive to or sensitized to. A typical material has a support coated with a red-sensitive silver halide emulsion with incorporated cyan dye-forming coupler, a green-sensitive silver halide emulsion with incorporated magenta dye-forming coupler and a blue-sensitive silver halide emulsion with incorporated yellow dye-forming coupler with one or more of my DIR hydroquinone compounds incorporated in one or more of the light-sensitive layers. The layers are advantageously coated in the order mentioned or in various other orders. The DIR hydroquinone compound is advantageously incorporated as an alkali metal salt, or in any of the well-known coupler solvents used in the art. When incorporated in a coupler solvent, the compound is incorporated along with the coupler in the same dispersion or in a separate coupler solvent dispersion or the compound is distributed between the coupler dispersion and separate dispersion. My DlR hydroquinone compounds are usually used in a light-sensitive layer where it is desired to have the image development in that layer (during color development) form an imagewise pattern of development inhibitor that diffuses into the adjacent 1ayer(s) and inhibits the color development of the latent images according to the mentioned imagewise pattern. This interimage effect is valuable for various purposes including masking unwanted light absorption in one or more of the image dyes. In addition to this effect, there is a valuable increase in sharpness at the edge of the dye images. My DIR hydroquinone compounds are particularly advantageously used because the same compound can be used not only in each image-forming layer but in interlayers as well, if desired, to produce a uniform increase in sharpness of each of the dye images, since these compounds are not only colorless but do not form dyes. Where different degrees of the interimage effect or the edge effect are desired different DlR hydroquinone compounds are used.

Any of the usual supports used in photographic materials can be used to advantage in making mu photographic elements including such typical supports as cellulose nitrate film, cellulose acetate film, polyvinyl acetal film, polystyrene film, polyterephthalate film, polyethylene film, polypropylene film, polyethylene-coated paper, paper, glass and others.

Any of the hydrophilic colloids used in the preparation of photographic elements are used to advantage in preparing the layers of my photographic materials. Illustrative examples include gelatin, colloidal albumin, cellulose derivatives or synthetic resins, such as, polyvinyl alcohol, etc.

The silver halide emulsion, preferably of camera speed, used in the first light-sensitive layer can be any silver halide emulsion used in photography, e.g., silver chlorobromide, silver bromoiodide, silver chlorobromoiodide, etc., preferably silver bromoiodide and an emulsion that is coarser grained and slower developing than the emulsion used in the second light-sensitive layer. Silver chloride when present usually comprises a smaller percent of the silver halide than in the second layer.

The silver halide emulsion used in the second light-sensitive layer 18 advantageously a finer grained rapidly developing silver halide emulsion, e.g., silver chlorobromide, silver chlorobromoiodide, etc., and is preferably of camera speed.

The same silver halide emulsion is advantageously used in each of the three layers of an element designed for color photography providing they are given appropriate spectral sensitization for the particular layer they are to be used in.

My emulsions are unfogged negative acting and when my elements containing them are developed in DK 50 developer solution for 5 minutes at 68 F. followed by fixing in conventional hypo fix bath, washing and drying, they produce a density in unexposed areas of not more than about 0.1 density units.

My camera speed emulsions have A.S.A. exposure indices of at least 10. The emulsions which are spectrally sensitized in my photographic elements are advantageously spectrally sensitized with cyanine and merocyanine dyes, such as those described in Brooker U.S. Pat. Nos. 1,846,301 and 1,846,302; and 1,942,854; White U.S. Pat. No. 1,990,507; Brooker and White U.S. Pat. Nos. 2,112,140; 2,165,338; 2,493,747; and 2,739,964; Brooker et al. U.S. Pat. No. 2,493,748, issued Jan. 10, 1950; Sprague U.S. Pat. Nos. 2,503,776, issued Apr. 11, 1950, and 2,519,001, issued Aug. 15, Heseltine et al. U.S. Pat. No. 2,666,761, issued Jan. 19, 1954; Heseltine U.S. Pat. No. 2,734,900, issued Feb. 14, 1956; VanLare U.S. Pat. No. 2,739,149, issued Mar. 20, 1956; and Kodak Limited British Pat. No. 450,958, accepted July 15, 1936.

The photographic silver halide emulsions and other layers on my photographic elements can contain any of the addenda generally utilized in photographic elements including speedincreasing materials, antifoggants, coating aids, gelatin hardeners, plasticizers, ultraviolet absorbers and the like.

The DlR development inhibitor-releasing hydroquinone compounds used in my photographic elements release development-inhibiting mercaptans that are diffusible in the layers of my photographic materials. 1t is believed that the DlR hydroquinone compound cross-oxidizes with the oxidation product of primary aromatic amine color-developing agents. As a result of this cross-oxidizing reaction. the hydroquinone is oxidized to the corresponding quinone. It is from this quinone only that the diffusible development-inhibiting mercaptan is split and released.

The DlR compounds of my invention are nondiffusible. or ballasted, heterocyclic thio-substituted hydroquinoncs which react with oxidized color-developing agent to form a diffusible mercaptan development inhibitor. The heterocyclic radical of the heterocyclic thio substituents are carbon-containing radicals generally having from four to six atoms in the ring with at least one heteronitrogen, oxygen, sulfur, or selenium atom and preferably from one to four heteronitrogen atoms. If desired, thio-substituted hydroquinone compounds of this invention can be masked with an alkaline-splittable group, that is, one or both of the hydroxyl groups of the hydroquinone can be replaced with any suitable substituent, such as, an acyl group which splits off under alkaline conditions to regenerate the hydroxyl group. A masking group inactivates a hydroxyl group of the hydroquinone compound. Masked hydroquinone com pounds can be incorporated directly in light-sensitive silver halide systems. The DlR hydroquinone compounds used advantageously in my invention include the compounds having the formula:

(t -Ball 8- Bad wherein Q is a hydrogen atom or an alkaline splittahle musk ing group, such as, an acyl group, e.g., acctyl. mono di, or

tri-chloroacetyl, mono-, di-, or tri-fluoroacetyl, fluoroacyl, pyryvyl, alkoxyalkyl, nitrobenzoyl, cyanobenzoyl, etc.; Q represents any of the members defined for Q; S- is a monothio radical which is split from the DIR compound when the said compound cross-oxidizes with oxidized color developer; Rad" represents a wide variety of photographically inert carbon-containing heterocyclic radicals that are diffusible in the layers of my photographic materials and form mercaptan with the monothio connecting or linking radical when the connecting radical is split from the quinone of the DIR hydroquinone compound; these heterocyclic radicals generally contain at least one heteronitrogen, oxygen, sulfur, or selenium and preferably one to four heteronitrogen atoms with no hydrogen atom attached to nitrogen atom(s). The photographically inert Rad radical of the formula includes heterocyclic radicals, such as, a l-phenyltetrazolyl, (e.g., l- (alkylphenyl)tetrazolyl in which the alkyl group has from one to four carbon atoms, a l-(alkoxyphenyl)tetrazolyl in which the alkyl moiety has from one to four carbon atoms, a l- (halophenyl)tetrazolyl in which the halogen is chlorine, bromine, fluorine, iodine, etc., a l-(nitrophenyl)tetrazolyl), an oxazolyl (e.g., 4-methyloxazolyl, S-methoxyoxazolyl, etc.), a benzoxazolyl (e.g., benzoxazolyl, S-methylbenzoxazolyl, 5- chlorobenzoxazolyl, 6-ethoxybenzoxazolyl, etc.), an anaphthoxazolyl (e.g., a-naphthoxazolyl, B-naphthoxazolyl, etc.), oxadiazolyl, a diazolyl, a thiadiazolyl (e.g., 5- methylthiadiazolyl, S-propylthiadiazolyl, etc.), a thiazolyl (e.g., thiazolyl, 5-methylthiazolyl, S-chlorothiazolyl, etc.), a benzothiazolyl (e.g., benzothiazolyl, S-ethoxybenzothiazolyl, -chlorobenzothiazolyl, S-methoxybenzothiazolyl, etc.), a naphthothiazolyl (e.g., a-naphthothiazolyl, [3- naphthothiazolyl, etc.). an imidazole, a benzimidazole (e.g., benzimidazole, o-chlorobenzimidazole, S-methpxybenzimidazole, S-methoxybenzimidazole, etc.), a pyrimidyl, a pyridinyl (e.g., pyridinyl, 3-methylpyridinyl, 4chloropyridinyl, S-ethoxypyridinyl, etc.). a quinolinyl (e.g., quinolinyl, 4- chloroquinolinyl, S-methoxyquinolinyl, etc.), and the like. The Ball in the above formula is a ballast group that's a photographically inert, organic radical of such molecular size and configuration as to render DIR hydroquinone compouhds nondiffusing in my photographic materials in the alkaline color development solution, and 0, represents the hydrogen atom, the SO M group, the COOM group; M represents a hydrogen atom or an alkali metal atom, e.g., sodium, potassium, lithium, etc.; Q and 0 each represent the same or different member such as hydrogen, alkyl having from one to carbon atoms (e.g., methyl, ethyl, octyl, decyl, etc.).

Specific examples of DIR hydroquinone compounds used to illustrate are as follows:

1. 2-{ 4-[ 3-( 4-tert-amylx-sulfophenoxy )benzamido] phenthyl}-x-( lphenyl-S-tetrazolythio)hydroquinone sodium salt 5-[4-( 3,5-disulfobenzamido )phenethyl ]-2-methyl-3-( lphenyl-S-tetrazolythio )hydroquinone disodium salt 3. 2- [4-[2-(2,4-di-tert-amylphenoxy )-5-(3,5-disulfobenzamido)benzamido1phenethyl] -x-( l-phenyl-S- tetrazolylthio)hydroquinone disodium salt dihydrate 2-{ 4-[ 3 4tert-amyl-x-sulfophenoxy)benzamido] phenethyl} -x-( lphenyl-5-tetrazolylthio)hydroquinone diacetate sodium salt dihydrate 5. 2-[4-(3,S-disulfobenzamido)phenethyl]-x-(l-phenyl-S- tetrazolythio)hydroquinone disodium salt dihydrate 2-[4-(3,S-disulfobenzamido)phenethyl]-x-(2-benzoxazolylthio)hydroquinone disodium salt dihydrate 7. 2,5-dimethyl-3-octadecyl-6-(lphenyl-S-tetrazolylthio)- hydroquinone 8. 2,5dimethyl-3-pentadecyl-6-( Z-benzothiazolylthio hydroquinone 2-{ B-[ 5-(B-carboxypropionamido )-2-( 2,4-di-t amylphenoxy)-benzamido]ethyl 3,5-dimethyl-6-( 2-oxadiazolythio)hydroquinone l0. 2-{4-[2-(2,4-di-t-amylphenoxy)-5-( 3,5-disulfamylbenzamido)benzamidolphenethyl}- 3,5-dimethyl-6-(5- methyl-2thiadiazolythio)hydroquinone 4 l l. 2.5-diethyl-3-pentadecyl-6(2-benzoselenazoly(thio)- hydroquinone The 1 used in the names of some of the illustrative compounds indicates that the substituent can be in any available position on the hydroquinone nucleus.

Many of the DIR hydroquinone compounds of my invention are described in US. Pat. No. 3,364,022 where a detailed, specific synthesis is given in column 13 for a representative compound no. 1. The other compounds included in formula I which are not specifically shown by the reference patent are prepared by methods well known in the art and need not be discussed further herein.

Any of the conventional four-equivalent or two-equivalent nondiffusing couplers used in photographic elements are used to advantage in the light-sensitive layers of my photographic materials, however, it is preferred to use the two-equivalent couplers. For certain effects it is advantageous to use colored color-forming couplers and/or development inhibitor releasing (DIR) couplers alone or in addition to the colorless couplers together with the DIR hydroquinone compounds.

The open-chain active methylene-containing couplers used to advantage include the cyanoacetyl couplers, such as the cyanoacetylcoumarone couplers, the cyanoacetylbenzoyl couplers, the heterocyclicacetonitrile couplers, etc., the openchain ketomethylene couplers, such as, the acylacetyl couplers (e.g., the acylacetanilide couplers, the acylacetamide couplers, etc.). The acylacetanilide couplers include the alkoylacetanilide couplers, the aroylacetanilide couplers. the pivalylacetanilide couplers, etc. The acylacetamidc couplers include the alkoylacetamide couplers, the aroylacetamide couplers, the pivalylacetamide couplers, etc.

These four-equivalent open-chain couplers include those represented advantageously by the formula:

RJI JCII X ballasting groups are very well known in the artv Whendesired, the ballasting groups are provided with solubilizing groups.

Typical four'equivalent yellow-forming couplers include the following:

Namylp-benzoylacetaminobenzenesulfonatc N-(4-anisoylacetaminobenzenesulfonyl )-N-benzyl-mtoluidine N-(4benzoylacetaminobezenesulfonyl)-N-benzyl-anilinc w p-benzoylbenzoyl )acetanilide w-benzoyl-p-sec.-amylacetanilide N,N-di(m-benzoylacetyl)-p-phenylenediamine .a- {3-[a-(2,4-di-tert-amylphenoxy)butyramido l-benzoyll 2-methoxyacetanilide 8. 4,4'-di-( acetoacetamino)-3,3-dimethyldiphenyl 9. p,p-di-(acetoacetamino)diphenylmethane l0. nonyl-p-benzoylacetaminobenzencsulfonate l l. N-phenylN-(p-acetoacetaminophenyl)urea l2. n-propylp-benzoylacetaminobenzcncsulfonatc acetoacetpipertdide l3. N(m-benzoylacetyl) l ,2,3,S-tetrahydroquinoline l4. N(m-benzoylacetyl)morpholine The two-equivalent yellow forming couplers are derived from the types of parent four-equivalent couplers by replacing one of the two hydrogens on the aplha-carhon (LC methylene) with any nonchromophoric coupling off group m eluding groups such as the fluorine atom. the chlorine atom, an acyloxy group, a cyclooxv group and a thlocyano group Typical two-equivalent couplers used to advantage included the alpha-fluoro couplers of U.S. Pat. No. 3,277,155, the achloro couplers of U.S. Pat. No. 2,778,658, the a-thiocyano couplers of U.S. Pat. No. 3,253,924, the a-acyloxy couplers of Loria U.S. Pat. application Ser. No. 477,353, filed July 26, 1965, the a-cyclooxy couplers of Loria U.S. Pat. application Ser. No. 469,887, filed July 6, 1965. and the a-alkoxy couplers of the type shown in Whitmore et al. U.S. Pat No. 3,227,550.

The two-equivalent open-chain yellow-forming couplers include those represented by the formula:

III.

wherein R and X are as described previously; Y is a coupling off group, such as, the chlorine atom, the fluorine atom, the thiocyano group, an acyloxy group [e.g., an alkoyloxy group (substituted or not), an aroyloxy group (substituted or not), a heterocycloyloxy group (substituted or not), etc., in which the groups are substituted with a wide variety of well-known groups and also a group in which R and X are as described previously], and a cyclooxy group [e.g., an aryloxoy group (e.g., a phenoxy group, a naphthoxy group, a heterocycloxy group (e.g., a pyridinyloxy group, a tetrahydropyranyloxy group, a tetrahydroquinolyloxy group, etc.)], an alkoxy group, a alkthio group and an arylthio group in which these groups are advantageously substituted with a wide variety of well-known groups and also :1

group in which R and X are as defined previously.

Typical illustrative examples of two-equivalent yellowforming couplers include the following:

1. 4-(a-2'-methoxybenzolyl-a-chloroacetamido)-3 -(4- tert.-amylphenoxy)benzanilide a-o-methoxybenzoyl-a-chloro-4-[a-(2,4-di-tertamylphenoxy )-n-butyramido ]-acetanilide 3. a l3-[a-(2,4-di-tert-amylphenoxy)butyramido1benzoyl} a-fluoro-2-methoxyacetanilide a-fluoro-a-pivalyl-S-E 2,4-di-tert-amylphenoxy)butyramidol-2-chloroacetanilide 5. a-acetoxy'a- {3-l'y 2,4-di-tert-amylphenoxy )butyramido ]benzoyl 2-rn ethoxyacetanilide 6. a-benZyl-a-[a-( 2 ,4-di-n-amylphenoxy)acetoxy1-2- methoxyacetanilide 7. a-pivalyl-a-stearoyloxy-4-sulfamylacetanilide 8. a-pivalyl-aa-( 3 -pentadecylph enoxy )acetoxy 1- 3 5 stituted S-pyrazolone couplers that are incorporated in photographic emulsion layers are used to advantage.

The 4-equivalent magenta-forming couplers used according to my invention includes those having the formula:

wherein R is as described previously and R represents a group such as an alkyl group, a substituted carbamyl group, an amino group (substituted or not with one or two alkyl groups and/or one or two aryl groups), a substituted amido group e.g., a benzamido group (substituted or not), an alkamido group (substituted or not), etc. The R and/or R groups are advantageously substituted with any of the well-known substituent groups used in color-forming couplers including ballasting groups to render the couplers nondiffusible in hydrophilic colloid layers, and solubilizing groups.

Typical illustrative examples of 4-equivalent magenta-forming couplers include the following:

I. l-p-sec.-amylphenyl-3-n-amyl-5-pyrazolone 2. Z-cyanoacetyl-S-)p-sec.-amylbenzoylamino)coumarone 3. 2-cyanoacetylcoumarone-5-(N-n-amyl-p-tert.-amy|- sulfanilide) 4. 2-cyanoacetylcoumarone-S-sulfon-N-n-butylanilide 5. 2-cyanoacetyl-5-benzoylamino-coumarone 6. 2-cyanoacetylcoumarone-5-sulfondimethylarnide 7. 2-cyanoacetylcoumarone-S-sulfon-N-methylanilide 8. 2-cycanoacetylcoumarone-5-(N--yphenylpropyl(-p-tert.

amylsulfonanilide 9. l-p-laurylphenyl-3-methyl-5-pyrazolone l0. l-B-naphthyl-3-amyl-5-pyrazolone l-p-nitrophenyl-3-n-amy|-S-pyrazolone l-p-phenoxyphenyl-3-n-amyl-5-pyrazolone l-phenyl-3-n-amyl-5-pyrazolone 1,4-phenylene bis3-( l-phenyl-S-pyrazolone) l-phenyl-3-acetylamino-S-pyrazolone l-phenyl-3-nvalerylamino-5-pyrazolone l-phenyl-3-chloroacctylamino-S-pyrazolone l-phenyl-3-benzoylamino-S-pyrazolonc l-phenyl-3-(m'aminobenzoyl)amino-S-pyrazolone l-phenyl-3-(p-sec.-amylbenzoylamino)-5-pyrazolonc l-phenyl-3-diamylbenzoylamino-S-pyrazolone 1-phenyl-3-B-naphthoylamino-S-pyrazolone l-phenyl-3-phenylcarbamylamino-S-pyrazolone l-phenyl-3-palmitylamino-5-pyrazolone 1-phenyl-3-benzenesulfonylamino-5-pyrazolone 26. l-(p-phenoxyphenyl)-3 (p-tert-amyloxybcnzoyl)amino- S-pyrazolone 27. l-(2,4',6-trichlorophenyl)-3-benzamido-5pyrazolonc 28. l 2',4',6-tribromophenyl )-3-phenylacetamido-5- pyrazolone 29. l-(2',4-dichlorophenyl)-3-l3"-(2"',4"'-di-tertamylphenoxyacetamido)benzamidoih-S-pyrazolone 30. l-(2',4',6'-trichlor0phenyl)-3-[3"-(2"',4"'-di-tert.-

amylphenoxyacetamido)benzamido]-5pyrazolonc 31. l-(2',4,6'-trichlorophenyl)-3-l B-( 2"',4"'-ditert.-

amylphenoxy)-propionamido l-5-pyrazolone 32. l-(2',5'-dichloro)-3-l3"-(4'"-terL-amylphcnoxy)benzamido1-5-pyrazolone 33. I -(2,4',6"tribr0mophenyl)-3-|3-(4"-tert.-

amylphenoxy)-benzamido]-5-pyrazol0ne 34 l-(2,5'-dichlorophenyl)-3[3"(2"'.4"'-di-tcrtamylphenoxyacetamido)benzamidoih-S-pyrazolonc The two-equivalent couplers are derived from the four equivalent parent couplers by replacing one of the hydrogens on the carbon in the 4-position of the pyrazolonc ring with a nonchromophoric coupling off group. Examples of coupling off groups used to advantage in two-equivalent magenta-forming couplers are the thiocyano group illustrated by the couplers in Loria U.S. Pat. No 3,252,924 and the acyloxy group containing two-equivalent magentaforming couplers of Loria U.S. Pat. No. 3,3l 1,476. The other coupling off groups include acyloxy, aryloxy, alkoxy such as are shown in Whitmore et al. US Pat. No. 3,227,550, the chlorine atom, the fluorine atom, and the sulfo group.

The two-equivalent magenta-forming couplers used according to my invention include those having the formula:

V. N= ?R' R-N I C-JIH-Y' wherein R and R' are as defined previously; and Y represents a coupling off group, such as, the thiocyano group, an acyloxy group, an aryloxy group, and alkoxy group, the chlorine atom, the fluorine atom, the sulfo group, etc.

Typical illustrative examples of two-equivalent magentaforming couplers include the following: j

l l-( 2,4,6-trichlorophenyl )-3-( 4-nitroanilino )-4- stearoyloxy-S-pyrazolone I 2. l-( 2,4,6-trichlorophenyl )-3-{ 3-[ a-( 2,4-di-tertamyphenoxy)-acetamido lbenzamido} -4-acetoxy-5- pyrazolone 3. -(2,4,6-trichlorophenyl)-3-pentadecyl-4-thiocyano-5- pyrazolone 4. l-(2,4,6-trichlorophenyl)-3-[ 3-(2,4-di-tert-amylphenoxyacetamido)benzamido]-4-thiocyano-5-pyrazolone 5. l-(p-tert-butylphenoxyphenyl)-3-a-(p-tert-butyl-phenoxy )-propionamido-4-thiocyano-5-pyrazolone 6. l-(2,4,6-trichlorophenyl)3-pentadeeyl-4-sulfo-5- pyrazolone f 7. l-( 2,4,6trichlorophenyl )-3-pentadecyl-4-chloro-5- pyrazolone I 8. 1-[4-(3,S-dicarboxylbenzamido) phenyl]-3-ethoxy-4-(3- octadecylcarbamylphenylthio)-5-pyrazolone Any of the well-known four-equivalent phenolic and naphthoic cyan-forming couplers can be used to advantage in my photographic materials. 1

The four-equivalent cyan-forming couplers used according to my invention include those having the formulas:

VI. OH

and VII.

wherein R represents hydrogen, an alkyl group, an aryl group, a heterocyclic group, an amino group (e.g., amino, alkylamino, arylamino, heterocyclic amino, etc.), a substituted carbonamido group (e.g., an alkylcarbonamido group, an arylcarbonamido group, and a heterocycliccarbonamido group), a substituted sulfonamido group(e.g., an alkylsulfonamido group, an arylsulfonamido group, a heterocyclicsulfonamido group, etc.), a substituted sulfamyl group (e.g., an aklylsulfamyl group, an arylsulfamyl group, a heterocyclic sulfamyl group, etc.), a substituted carbamyl group (e.g., an alkylcarbamyl group, an arylcarbamyl group, a heterocyclic carbamyl group, etc.), a halogen atom (e.g., chlorine, bromine, etc.), etc.; and R, R R each represent any of the groups represented by R and in addition an alkoxy group, etc., R, R", R and R are advantageously further substituted by any of the ballasting groups well known in the art.

Typical four-equivalent cyan-forming couplers include the 7 following illustrative examples:

1. 5-( p-amylphenoxybenzenesulfonamino l -naphthol 2. 5-( n-benzyl-N-n-valerylamino)- l -naphthol 3. S-caproylaminol -naphthol 4. 2-chloro-5-(N-n-valeryl-N-p-isopropylbenzylamino)-lnaphthol 5. 2-chloro-5-palmitylaminol -naphthol 6. 5-diphenylethersulfonamidol -naphthol 7. l-hydroxy-2-(N-isoamyl-N-phenyl)naphthamide 8. 8-hydroxyl -hydroxy-1 -a-naphthoyl- I ,2,3,4-

tetrahydroquinoline 9. l-naphthol-S-sulfo-cyclohexylamide l0. 5-phenoxyacetamino-l -naphthol Monochlor-S-(N -phenylpropyl-N-p-sec.-amylbenzoylamino l -naphthol l2. 2-benzoylamino-3,5-dimethylphenol l3. Z-a-(p-tert-amylphenoxy )-n-butyrylamino-5- methylphenol l4. l-hydroxy-N-[o'-(2,4-di-tert.-amylphenoxy)butyl1-2- naphthamide l5. 2-(4-tert.-amyl-3-phenoxybenzoylamino)-3,5'

dimethylphenol l6. 2(4-tert.-amyl-3-phenoxybenzoylamino)phenol l7. 2-[a-(4-tert.-butylphenoxy)propionylaminolphenol l8. 2-lN-methyl-N-(4-tert.-amyl-3-phenoxybenzoylamino)]phenol l9. 2-a-(4-tert.-amylphenoxy)butyrylaminol -phenol 20. 2-(4-tert.-amyl-3-phenoxybenzoylamino)-3,5-

dimethylphenol 21. 2-[rx-(4-tert.-amyphenoxy)-n-butyrylamino]-5- methylphenol 22. 3-(4-tert.-amyl-3'-phenoxybenzoylamino)phenol 23. 2-[a-(4-tert.-amylphenoxy)-n-butyrylamino]-6- chlorophenol 24. 3-[a-(4-tert.-amylphenoxy)-n-butyrylamino1-5- chlorophenol 25. 5-benzene sulfonamidol -naphtho| 26. 2-chloro-5-benzenesulfonamidol -naphthol 27. 5-( l,2,3,4-tetrahydronaphthalene-6-sulfonamido)- l naphthol 28. 2-chloro-5-(4-bromodiphenyl-4-sulfonamido l naphthol Any of the well-known two-equivalent cyan-forming couplers known in the art for incorporation in photographic layers may be used to advantage. Usually the two-equivalent couplers are derived from the corresponding four-equivalent couplers by substituting a nonchromophoric coupling off group on the carbon in the 4-position of the phenolic or naphthoic ring. Included among the coupling off groups are the acyloxy group illustrated by the 4-acyloxyphenols and 4 acyloxynaphthols of Loria U.S. Pat. No. 3,3ll,476, issued Mar. 28, 1967, the cyclooxy group illustrated by the 4- cyclooxy naphthols of Loria U.S. Pat. application Ser. No. 483,807, filed Aug. 30, I965, the thiocyano group illustrated by the 4-thiophenols and 4-thionaphthols of Loria U.S. Pat. No. 3,253,294, the cyclic imido groups as illustrated by the 4- cyclic imido derivatives of l hydmgen-Z-naphthamides of Loria U.S. Pat. application Ser. No. 504,994, the chlorine atom as illustrated in the 4-ehlorophenols ofWeissberger U.S. Pat. No. 2,423,730, the alkoxy group as illustrated by the 4-alkoxynaphthols of Whitmore et al. U.S. Pat. No. 3,227,550, the sulfo group as in 4-4-sulfophenols and 4-sulfonaphthols, etc.

The two-equivalent cyan-forming couplers used according to my invention include those having the formulas:

and 1X.

VIII.

2. l-hydroxy-4-acetoxy-N-[a-(2,4-di-tert-amylphenoxy)bu tyl]-2-naphthamide 3. l-hydroxy-4-acetoxy-N-octadecyl-3 ',5 '-dicarboxy-2 naphthanilide 4. l-hydroxy-4-thiocyano-N-l01-2,4-di-tert-amylphenoxy)- butyl]-2-naphthamide tert-aylphenoxy )acetamido ]phenyl} ethyl }-2-naphtha' mide 6. 1-hydroxy-4-( 4-nitrophenoxy )-N-[ 01-2 .4-di-te rt amylphenoxy)butyl]-2-naphthamide 7. l-hydroxy-4-(4-chlorophenoxy)-2'-tetradecyloxy-2- naphthanilide The colored color-forming couplers used according to my invention are represented by formulas 111, V V111 and IX in which the Y, Y', Y and Y groups respectively are not as defined previously but are groups which contain a chromaphore such as an arylor heterocyclic azo group. Representative colored color-forming couplers are described by patents such as Vittum et al. U.S. Pat. No. 2,428,054; Hanson U.S. Pat. No. 2,449,966; Glass et al. U.S. Pat. No. 2,453,661; Vittum et a1. U.S. Pat. No. 2,455,169; Glass et al. U.S. Pat. No. 2,455,170; Glass et al. U.S. Pat. No. 2,521,908; Graham et al. U.S. Pat. No. 2,657,134; Beavers US. Pat. No. 2,983,608; Saunders et al. U.S. Pat. No. 3,005,712; and Gladhill et al. U.S. Pat. No. 3,034,892.

The DIR couplers used to advantage in my photographic elements include those described by such U.S. Pat. Nos. as 3,148,062; 3,227,554, etc.

The ballasted DlR hydroquinone compounds and couplers used in my invention are advantageously dispersed in highboiling, crystalloidal compounds which can be used as a vehicle for incorporating the compounds and coupler in the photographic cmulsion according to methods well known in the art. Various other known methods of incorporating the DIR hydroquinone compounds and color forming couplers in our element are also utilized. For example, the low solvent dispersions described in Fierke U.S. Pat. No. 2,801,107 are used to advantage; or the compounds and couplers are dispersed in natural resin-type solvents as described in Martinez U.S. Pat. No. 2,284,877, or the compounds and couplers are dissolved in monomeric solution which is then polymerized in the presence of gelatin to produce dispersions of the coupler in the polymer as described in U.S. Pat. No. 2,825,382. Altematively, the MR hydroquinone compounds and/or color-forming couplers can be of the "fat-tail" variety, that is, the Fischer type which have solubilizing groups on them which render them soluble in alkaline solution.

The term nondiffusing used herein as applied to the DIR hydroquinone compounds, has the meaning commonly applied to the term in color photography and denotes materials which for all practical purposes do not migrate or wander through organic colloid layers. such as gelatin. comprising the sensitive elements of the invention. The term diffusible" as applied to the mercaptan development inhibitors released from the DlR compounds denotes materials having the property of diffusing effectively through the colloid layers of the sensitive elements in the presence of the nondiffusing" materials from which they are derived in alkaline colordeveloping solutions.

The selection of the particular DIR hydroquinone compound(s), coupler(s) and optical sensitizing dye(s) (when needed) for use in my elements will depend upon the particular use for which the material is to he designed The important thing is that the first light-sensitive layer records only one image and the second light-sensitive layer records only another image and that the latent image in one layer is reproduced as a visible image that IS vividly different than the latent image reproduction in the other layer The DlR hydroquinone compounds of my invention are advantageously used over a wide range 01 coating rates usually about 2 mg./ft. or more, and preferably in the range from about 5 mgJlt. to about 100 mg./ft 2 The optimum coating rate will depend upon the particular emulsions used and the results desired. The optimum rates are easily determined by methods well known in the art.

In the photographic elements of my invention that use a bleachable light-filtering layer between the two light-sensitive layers to confine the image exposures to the appropriate layers, any of the well-known removable light-absorbing dyes having the desired light-absorbing characteristics may be used. Preferably, these dyes are water-soluble dyes which have acid substituents on them, e.g., sulfo, sulfoalkyl, carboxy, carboxyalkyl, etc., or dyes that have dialkylaminoalkyl substituents on them so the dyes are washed out of the emulsion during photographic processing. Other dyes used to advantage are bleached by the alkaline sulfite in the developer solutions or the thiosulfate ion in the hypo fix bath during the photographic processing, Included among light-absorbing dyes used to advantage are the cyanines, merocyanines, styryl, cinnamylidene, oxanol dyes, etc., such as those described in U.S. Pat. Nos. 2,298,733; 2,537,472; 2,622,082; 2,691,579; 2,843,486; 2,856,404; 3,247,127; etc. These dyes have no appreciable effect on the sensitivity of the silver halide, that is, they are neither sensitizers or desensitizers so that it is not necessary to use mordants to hold them precisely in the filter layer, how ever, it may be advantageous to use appropriate mordants, for example, basic mordants, such as are described in Minsk U.S. Pat. No. 2,882,156 for mordanting dyes having acid substitutents. Illustrative dyes which are used to advantage in my elements include the following:

Dye

No Dye Name 1 Bis(l-n-butyl 3-carboxymclhylhcxadydro-2,4,6

trioxu-Spyrimidinc)pentamethinoxonol 2 Bis( l-carboxymethylhexahydro-Il-phcnyl 2,4,6

triOxoS-pyrimidine)pcntamcthinoxonol 3 Dist 1 n-butyl-3 cnrhoilymethylhexahydro-Z 4,h

trioxo-S-pyrimidine Jtnmcthinoxonol 4 Bis( l -carboxymethylhexahydrod-n-octyl 2 4,h

trioiro-S-pyrimidine )mclhinoxonol 5 Anhydro chlortr9 ethyl-3 mcthyl l (l sullobutyl)-4,5-bcnzolhiacarbocyanmc hydroxtde, monusull'unalcd 6 Anhydro-3 3'-dicthyl-9-mcthyl4,5; 4'.5'-

dibenzothiacarbocyaninc hydroxide disulfonatcd 7 Anhydro -cthyl-3,3'-dimcthyl-4,5; 4 5

dibcnzothiacarhocyanine hydroxide, disull'onatcd 8 Anhydro-3,3', 9-tricthyl5,5'-di(p-sull'ophcnyl) oxacarbocyanine hydroxide 9 Anhydro-l ,l '-dicthyl- 2,2'-cyaninc hydroxide,

munosulfonatcd 4-|(3 cthyl2-(3H)-ben1oxazolylidcne)cthylidcnc| 3 methyl- I -p-sull'ophcnyl-pyr:|zolin-5 onc monosulfonated 4 [4-(3elhy|-Z-( 3H J-bcnzoxalolylrdctlc) 2 butenylidcncl-J-mcthyl-l-p-sulfophcnyl 2 pyrazolm-S-onc, monosulfonated Colloidal silver, such as, Carey-Lea silver dispersed in gelatin is advantageously used in place of blue light-absorbing dyes in my photographic element. This filter material is well known in the art and is removed by the bleaching and fixing steps during photographic processing.

Any of the oxidized color-developing agent scavengers known in the prior art may be used to advantage in the light filtering layer between the first and second light-sensitive emulsion layers. Particularly efficacious for this purpose are the ballasted hydroquinones such as'the higher alkyl sub stituted hydroquinones in which the alkyl groups have from seven to 22 carbon atoms. e.g., dioctyl hydroquinone, didodecyl hydroquinone, dipentadecyl hydroquinone, didocosyl hydroquinone. ett The DlR hydroquinone compounds of my invention are also used advantageously in inter layers to obtain a development-inhibiting affect in addition to the above-mentioned scavenging effect My photographic elements are developed with photographic alkaline color developer solutions containing any of the primary aromatic amino color-developing agents used in color photography including p-phenylenediamines, such as. 3- acetamido-4-amino-N,N-diethylaniline, P-amino-N-ethyl-N- B-hydroxyethylaniline sulfate. p-aminoethyl-B-hydrox yethylaniline, N.N-diethyl-p-phenylenediamine, Z-amino-S- diethylaminotoluene, N-ethyl-B-methylsulfonamidoethyl- 3- methyl-4-aminoaniline, 4-amino-N-ethyl-3-methyl-N-(B-sulfoethyl)aniline and the like Reference is made to Bent et al. J.A.C.S., 73, 3,l3.l25 1951) for additional typical suitable color-developing agents. Benzyl alcohol, ascorbic acid, alkali metal bromide, alkali metal thiocyanate, alkali metal thiosulfate, competing coupler, auxiliary developers and other addenda used in color-developing solutions are also used to advantage in my color developers.

The following examples are included for a further understanding of my invention.

EXAMPLE I A piece of transparent cellulose acetate film support is coated with a coarse grain blue-sensitive camera speed gelatino silver bromoiodide emulsion containing the coupler, l-(2,4,6-trichlorophenyl)-3-pentadecyl-4-chloro-5- pyrazolone. Over this layer is coated a rapid developing fine grain green-sensitized gelatino silver chlorobromide emulsion containing the cyan dye-forming coupler, 2-[a(3-pentadecylphenoxy )butyramido]-5-methoxy-phenol and the DIR hydroquinone compound No. 9, i.e., 2-l B-[S-(B-carboxypropionamido )-2-( 2,4-di-t-amylphenoxy )benzamido lethyl} 3,5-dimethyl-6-(2-oxadiazolylthio)hydroquinone. The gelatino silver halide emulsions used above are made as described by Trivelli and Smith Photo. Journal, 79, 330 (1939). After drying, this element is exposed to the optically combined registered light images from an SLR radar scope having blue-light-emitting phosphors in and an MTl radar scope having green-light-emitting phosphors in its screen. The map image from the SLR radar scope is recorded in the first light-sensitive layer and the moving target image is recorded in the second light-sensitive layer. A developing solution having the following composition:

Benzyl alcohol l0 ml N-hydroxyethyl-N-ethyl-p-aminoaniline-hydrogen sulfate monohydrate l0 g. Sodium carbonate monohydrate 20. g. Sodium sultite 50. Potassium bromide 0.75 g. Distilled water to l l. Sodium hydroxide to pH l 1.0

is applied to the top or second light-sensitive layer. Upon penetration of the developing solution, the top layer of the film produces a silver and cyan dye image from the latent image of the MTl and liberates phenyl mercaptotetrazole which accompanies the developer solution in an imagewise pattern into the first light-sensitive layer where a silver and magenta dye image is formed of the SLR latent image excepting under the areas where images are formed in the top second light-sensitive layer where no developed image is formed (in the first light-sensitive layer). The developed photographic material is EXAMPLE immersed in a conventional potassium ferricyanide, potassium bromide bleach solution followed by a conventional sodium thiosulfate hypo fix leaving only bright cyan dye images of the MT] in the top layer and a magentacolored image of the SLR map in the bottom layer. No magenta image is formed directly under and slightly outside the cyan dye images even in areas where a latent image was recorded in the first light-sensitive layer. Even very minute MTl cyan color images are very easily discernible in the processed film because of the bright cyan dye enhanced by the clear area surrounding it.

Example 2 A material is coated like that described in example 1 excepting that no color-forming coupler is used in the first lightsensitive layer. This material is exposed and color developed as described in example I, then treated with a stabilizing solution containing thiourea in order to stabilize the unexposed. undeveloped silver halide so that it will not print out on exposure to light. Good readily discernible cyan dye images which are formed in this element are surrounded by the underlying silver image in the first light-sensitive layer. This very rapidly produced image reproduction can be studied and sub sequently fixed with sodium thiosulfate fixing bath to remove the unexposed, undeveloped silver halide.

EXAMPLE 3 A photographic material is made like that described in example l excepting that a green-sensitized silver chlorobromoiodide emulsion is used in place of the blue-sensitive silver bromoiodide in the first light-senstive layer and a lchlorobromide emulsion is used instead of the green-sensitized silver chlorobromide in the second light-sensitive layer.

This material is exposed using an SLR radar scope having a green-light-emitting phosphor and an MTl radar scope having a phosphor emitting blue light. Upon development, as described in example 1, this material produces images comparable to those in example I.

EXAMPLE 4 A photographic material is made similar to that described in example 1 excepting that the DIR hydroquinone compound No. 8, i.e., 2,S-dimethyl-3-pentadecyl-6-(2 benzothiazolylthio)-hydroquinone, is used in place of DIR hydroquinone compound No. 9. Similar results are obtained to those as obtained in example I from exposure and processing of this material as described in example 1.

EXAMPLE 5 A photographic material is made like that described in example l excepting that the coupler, l-hydroxy-4-acetoxy-N-l a-(2,4-di-tert-amylphenoxy)butyll-2-naphthamide is used in the first light-sensitive layer in place of the coupler, l-(2,4,6- trichlorophenyl l-3-pentadecyl-4-chloro-5-pyrazolone and the DIR hydroquinone compound No. 2, i.e., 5-]4-(3,5-disulfobenzamido)-phenethyl |-2-methyl-3-( l-phenyl-S- tetrazolylthio)hydroquinone disodium salt, is used in the second light-sensitive layer in place of the DlR hydroquinone compound No. 9. Upon exposure and processing as described in example I, there is produced vividly discernible magentacolored MTl images surrounded by a narrow, clear area outside of which is a cyan-colored SLR map image reproduction. As in the examples described before, there is no dye image in the first light-sensitive layer underneath the dye images in the second light-sensitive layer of the processed material.

EXAMPLE 6 A clear cellulose acetate film support is coated with a coarse grain blue-sensitive gclatino silver chlorobromide emulsion containing the coupler, 2-[a-(2,4-di-tertamylphenoxy )-butyramido I-4,6-dichloro-S-methylphenol. Over this first light-sensitive layer is coated a gelatin layer containing dioctyl hydroquinone and this layer is in turn coated with a fine grain rapidly developing green-sensitized gclatino silver chlorobromide emulsion containing the magenta dycforming coupler, l-l 4-( 2,4-di-tert-amylphenoxybutyramido)phenyll-3-cthoxy-5pyrazolone, and the development inhibitor releasing hydroquinone compound No. 10, Le 2-l4-[2-(2,4-di-t-amylphenoxy)-5-(3,5-disulfamylbenzamido)benzamido l-phenethyl} -3,5-dimethyl-6-( 5- methyl-2-thiadiazolylthio)hydroquinone. Upon exposure and processing as described in example 1, bright, readily discernible magenta dye images are obtained of the MTl surrounded by narrow, clear images which are in turn surrounded by a cyan-colored SLR map image EXAMPLE 7 l A photographic material is made similar to that described in example 6 but in which the gelatin layer between the first and second light-sensitive layers contains a colloidal Carey-Lea silver dispersion and a blue-sensitive silver chlorobromide emulsion is used in the second light-sensitive layer instead of the green-sensitized silver chlorobromide emulsion. This material is exposed through the support to the blue light image of the SLR map and through the second light-sensitive layer to an MTl from a blue light-emitting radar scope. The exposing images from the two radar scopes are positioned so that they are in register before the exposure is made. Upon processing, similar good results are obtained to those described in example 6.

EXAMPLE 8 A cellulose acetate film support is coated in succession on one side with (l) a layer containing a coarse grain green-sensitized gelatino silver chlorobromide emulsion, and the nondiffusible magenta dye-forming coupler, l-phenyl-3-{ 3-[d-(3- pentadecylphenoxy)-acetamido]benzamido}-5-pyrazolone dispersed in dibutylphthalate, (2) a gelatin layer containing 2- octadecyl-S-sulfohydroquinone potassium salt and (3) a layer containing a fine grain rapidly developing red-sensitized gelatino silver chlorobromide emulsion, DIR hydroquinone compound No. l, i.e., 2-{4-[3-(4-t-amyl-x-sulfophenoxy)benzamido]-phenethyl} -x-( l-phenyl-S- tetrazolylthio)hydroquinone sodium salt and cyan dye-forming coupler. l-hydroxy-N-[6-(2,4-di-t amylphenoxy)butyl ]-2- naphthamide dispersed in dibutylphthalate. One piece of the coated material described is coated on the support side away from the light-sensitive layers, with a removable antihalajtion backing. After drying, pieces of the photographic elements are exposed as described in example 1 excepting that SLR radar scope has a phosphor that emits green light and the MT] radar scope has a phosphor that emits red light. The exposed photographic elements are developed by contacting them with a developer solution having the composition: 1

N-Hydroxyethyl-N-ethyl-p-aminoaniline sulfate Ascorbic acid :05 g. Sodium carbonate 20. g. Potassium bromide 4. Sodium sulfite so Water to ll. pH adjusted to l l l The developer films are washed, then immersed in a conventional potassium ferricyanide, potassium bromide bleach solution followed by a conventional sodium thiosulfate hypo fix leaving a composite image of a bright cyan dye image of the MT] combined with a magenta dye image of the SLR map image. In those areas where the cyan image IS formed inj the top layer there is no magenta image formed directly underitt in the bottom layer. This example is repeated using DlR hydroquinone compound No 3 in place of compound No. l with similar results. The processing baths remove the antihalation layer from the photographic element that had this layer.

EXAMPLE 9 l l A photographic element is made similar to that made in example l excepting that a red-sensitive camera speed coarse grain gelatino silver bromoidide emulsion is used in place of the blue-sensitive silver bromoiodide emulsion in the first light-sensitive layer and the yellow dye-forming coupler, a[4- (hydroxy-phenylsulfonyl)phenoxyl-a-pivalyl Z-chIoro-S-[ (2,4-di-tert-amylphenoxy)butyramido]acctan|lide is used in place of the magenta-forming coupler. l-(2,4,6- trichlorophenyl)-3-pentadecyl-4-chloro 5 -p vrazolonc This material is used as described for example 1 excepting that the radar scope used for imaging the SLR map has a red-lightemitting phosphor screen. The processed material has bright cyan image reproductions of the MTl surrounded by a yellow dye image reproduction of the SLR map No yellow dye image IS produced directly under the cyan dye images.

EXAMPLE 10 A photographic element is made similar to that made in example excepting that blueand red-sensitive camera speed gelatino silver bromoiodide emulsion is used in place of the blue-sensitive emulsion coated on the support in example I. After drying, this element is exposed as described in example I except that the SLR radar scope phosphors emit blue light and red light (but no green light). Results similar to those obtained in example 1 are obtained when this exposed material is processed as described in example I. This example shows that light from two different regions of the actinic spectrum is used advantageously to record one image and light from a third and exclusively different region of the actinic spectrum is used to advantage to record the second image.

Similar results are obtained when still other parts of the actinic spectrum are used including the ultraviolet light, visible light and infrared regions of the spectrum.

EXAMPLE 11 A photographic element is made similar to that made in example excepting that an ultraviolet-sensitive camera speed gelatino silver bromoiodide emulsion is used in place of the blue-sensitive emulsion coated on the support and an infraredsensitized gelatino silver chlorobromide emulsion is coated over it instead of the green-sensitized emulsion used in example 1. After drying, this material is exposed and processed as described in example I excepting that the phosphor used in the SLR radar scope emits an ultraviolet light image and the phosphor used in the MT] radar scope emits an infrared light Image.

Similarly it can be shown that any of the other twoequivalent dye-forming couplers, as well as four-equivalent dye-forming couplers described in this application can be used advantageously in the first light-sensitive layer and that the DlR hydroquinone compounds illustrated in examples I through 2. as well as any of the other DlR hydroquinone com pounds described in this specification, can be used advantageously in the second light-sensitive layer. Although the examples show the use of gelatin as the hydrophilic colloid material for the layers of my photographic elements, it is understood that any of the other hydrophilic colloids used in photographic layers, especially those mentioned previously, can also be used to advantage. Any appropriate support materials used in photographic elements can advantageously be used in my photographic materials.

EXAMPLE 12 A piece of transparent cellulose acetate film support is coated in succession with l) a rapidly developing fine grain green-sensitized gelatino silver chlorobromide emulsion containing the DlR hydroquinone compound No 6, Le, 2-[4- (3,S-disulfobenzamido)phenethyll x-(2-benzoxazolylthio)hydroquinone disodium salt dihydrate, and 2-la (3-pentadecylphenoxy)butyramidol-5-methoxyphenol and (2) a coarse grain blue-sensitive camera speed gelatino silver bromoiodide emulsion containing the coupler l-(2,4,6- trichlorophenyl)3-pentadecyl-4-chloro-5-pyrazolone. This material is exposed and processed as described in example l giving results that are similar to those in example I.

EXAMPLF 13 A piece of the photographic material made in example 12 is coated over the outer light-sensitive layer with a third lightsensitive layer comprising a rapidly developing fine grain redsensitized gelatino silver chlorobromide emulsion containing DlR hydroquinone compound No. 6 and yellow coupler. aacetoxy-a- {EH- (2,4-di-t-amylphen0xy )butyramidolbenzoyll 2-methoxyacetanilide. The dried material is exposed as described in example I excepting that the material is also exposed to a red light image (placed in optical register with the other two light images) emitted by the phosphor of a cathoderay tube which is driven by electronic signals from an infrared sensing element that is scanning the same area being covered by the SLR and MT]. Upon processing as described in example l, cyan dye images representing the MTI and yellow dye images representing infrared radiating objects are vividly discernible against the magenta dye image of the SLR map. No magenta dye image is developed in the photographic material in areas where there is a cyan and/or a yellow dye image.

EXAMPLE 14 Film A is made by coating in succession on one side of a cel lulose acetate film support (I) a red-sensitized gelatino silver bromoiodide emulsion layer containing DIR hydroquinone compound No. l, i.e., 2-{4-[3-(4-t-amyl-x-sulfophenoxy)benzamido ]phenethyl }-x-( l-phenyl-S- tetrazolylthio)hydroquinone sodium salt and the nondiffusing cyan dye-forming coupler, l-hydroxy-N-[8-(2,4-di-tamylphenoxy)butyl]-2-naphthamide, (2) a gelatin layer, and (3) a green-sensitized gelatino silver bromoiodide emulsion layer containing the nondiffusing magenta dye-forming coupler, l-(2,4,6-trichlorophenyl)-3-{ 3-[a-(2,4-di-t-amylphenoxy)acetamido]-benzamido} -pyrazolone. Control Film B is made like Film A but contains no DIR hydroquinone compound. Films A and B are given red light exposures under a step tablet and each uniformly flashed to green light then color processed using the Processing Steps for Eastman Color Negative Film, Type 5248" described by Hanson and Kisner in Society of Motion Picture and Television Engineers, 61, pages 667-70I. Dec, I953 A comparison of the developed films shows that the development of the magenta dye image in Film A is decreased in proportion to the exposure and development in the underlying cyan layer and thus in proportion to the amount of development inhibitor released from compound No. 1. Improved image sharpness is particularly evident.

EXAMPLE Films C and D (control) are made like Films A and B (control) respectively in example 14 excepting that yellow-colored magenta dye-forming coupler, I-(2,4,6-trichlorophenyl)-3-l 3[a-(2,4-di-t-amylphenoxy )acetamido1benzamido l-4-(4- methoxyphenylazo)-5-pyrazolone is used in (3), the outer layer, in addition to the main magenta image-forming coupler, and red-colored cyan dye-forming coupler. I-hydroxy-4-(2- acetylphenylazo )-N-[ 8-( 2,4-di-t-amylphenoxy )butyl -2- naphthamide is used in (I), the first layer, in addition to the main cyan image-forming coupler. When Films C and D are exposed and processed as described in example 14 and compared, it is noted that the development of the magenta dye image in Film C is decreased in proportion to the exposure and development In the underlying cyan layer (as in Film A), also Films C and D show some color correction from the colored color-forming couplers.

EXAMPLE 16 Films E and F (control) are made like Films C and D respectively excepting that DIR coupler, l-hydroxy-N-[8-2,4- di-t-amylphenoxy)butyl ]-4-( l-phenyI-5-tetrazolylthio)-2- naphthamide is added to (l) and DIR coupler, l-{4-[a-(3- pentadecylphenoxy)butyramido1phenyl }-3-ethoxy-4-( lphenyl-S-tetrazolylthio)-5-pyrazolone is added to layer (3 When exposed and processed as described in examplel4, Film E shows not only the effect demonstrated by the DIR hydroquinone compound in Film A but also additional color correction provided by the presence of the colored colorforming couplers and the DIR couplers.

The DIR hydroquinone compounds of my invention can be used in color photographic coatings in combination with other DIR hydroquinone compounds of my invention as well as with diffusible or nondiffusible, colorless or colored, couplers which form nondiffusible or diffusible image dyes or leuco dyes, or any combination of such couplers. My DIR hydroquinone compounds also can be used in combination with diffusible or nondiffusible DIR couplers such as those described in US Pat. Nos. 3,227,554 and 3,148,062, either alone or in combination with any of the above-mentioned couplers. My DIR hydroquinone compounds are also advantageously incorporated in photographic coatings together with developer compounds such as, for example, hydroquinones, p-phenylenediamines, l-phenyl-3-pyrazolidones, as well as developing agent precursors of such compounds. My DIR hydroquinone compounds are also advantageously used in non-light-sensitive layers of a silver halide coating, e.g., interlayers, underlayers and overcoats, etc. i

As mentioned previously herein, some of my photographic elements advantageously form diffusible dyes that are transferred during the development step to a mordanted reception sheet. The reception sheet for receiving the diffusible dye images can be an integral part of the photosensitive element. A typical element of this type can comprise a support (any of those mentioned previously), a mordanted hydrophilic colloid layer thereon and the various light-sensitive layers described above coated thereover. It is advantageous to have a stripping layer comprising a layer containing polyvinyl alcohol or an alkali-soluble cellulose ether phthalate vehicle, or a wet or dry stripping layer between the mordanted layer and the first layer of the light-sensitive element so that the reception sheet can be easily removed after development. If the support is transparent, the light exposure can be made through it ifdesired. In elements of this type which have the reception sheet as an integral part and which not only form the transfer images but also nondiffusible dye images, it is advantageous after development to provide the image-forming layers with a permanent support; this is advantageously done at the time the reception sheet is stripped off. When the reception sheet is not an integral part of the element, a separate reception sheet is contacted with the outermost light-exposed light-sensitive layer of the photographic element in the presence of the developer solution and then separated after completion of development.

Any of the conventional mordant materials for acid dyes are advantageously used on the reception layer, including polymers of amino guanidine derivatives of vinyl methyl ketone described in the Minsk US. Pat. No. 2,882,156, issued Apr. I4, 1959 (which disclosure is incorporated herein by reference); the 2-vinyl pyridine polymer metho-p-toluene sulfonate and similar compounds described in Sprague et al. US. Pat. No. 2,484,430, issued Oct. I I, I949 (which disclosure is incorporated herein by reference); and cetyl trimethylammonium bromide; etc. Particularly effective mordanting compositions are described in Knechel et al. US. Pat, No. 3,27l,l48 and Bush US. Pat. No. 3,27l,l47, both issued Sept. 6, I966 (which disclosures are both incorporated herein by reference).

Any of the well-known nondiffusible couplers which form diffusible dyes are used advantageously in my photographic elements. Typical examples include the couplers which form diffusible dyes upon color development as described in Barr et al. US. Pat. No. 3,227,551, issued .Ian. 4, I966 (which disclosure is incorporated herein by reference). For example, in this reference Couplers I through X all react with oxidized primary aromatic amine colordeveloping agents to release diffusible yellow dyes and nondiffusing cyan dyes except VIII which forms a nondiffusible magenta dye and IX which forms a nondiffusible yellow dye, (ouplers XI to XXIX react with oxidized color-developing agent to form diffusible cyan dyes; Couplers XXX to XLI react with oxidized color-developing agent to form diffusible magenta dyes; and Couplers XLII to XLVI react with oxidized color-developing agent to form diffusible yellow dyes EXAMPLE 17 A photographic element is made like that described in example except that in addition to the coupler, 1-(2,4,6- trichlorophenyl)-3-pentadecyl-4-chloro-5-pyrazolone, coupler 1-(4-sulfophenyl )-3-( 4sulfoanilino)-4-(3-oetadecylcarbamylphenylthio)--pyrazolone disodium salt (Coupler XL in Barr et a]. US. Pat. No 3,227,551), is also coated in the coarse grain blue-sensitive emulsion, and in the fine grain green-sensitized emulsion Coupler XX of Barr et al. US. Pat. No. 3,227,551, i.e., l-hydroxy-4-(3-oetadecylcarbamylphenylthio)-N-ethyl-3',5'-di-carboxy-2-naphthamide is coated with coupler 2-[a-(3-pentadecylphenoxy)butramido]-5- methoxyphenol. The photographic element is exposed as described in example 1, a reception sheet comprising a cellulose acetate film support coated with a gelatin layer containing cetyl trimethylammonium bromide is moistened on the gelatin-mordant layer with the developer solution described in example 1 and this layer is firmly contacted with the outermost light-senisitve layer of the element until development is completed and then the reception sheet is separated from the developed element carrying in the mordanted layer a composite magenta dye image of the SLR latent image and cyan dye image of the MTl latent image. The developed photographic element has in it the silver and dye images described in example 1, and the processing of this element is completed as described in example 1.'The dye images in the reception sheet are ready for study as soon as the reception sheet is separated from the developed element, however, it is advantageous to remove residual developer solution from the reception sheet by any convenient method, e.g., water washing, squeezing, contacting with a dilute acid solution (e.g., dilute acetic acid solution), etc.

EXAMPLE 18 A photographic element is made like that described in example except that coupler l-(4-sulfophenyl)-3-(4-sulfoanilino)-4-(3-octadecylcarbamylphenylthio)-5-pyrazolone disodium salt is used in the coarse grain blue-sensitive emulsion instead of coupler l-(2,4,6-trichlorophenyl)-3-pen tadecyl-4-chloro-5-pyrazolone, and coupler l-hydroxy-4-(3- oetadecylearbamylphenylthio)-N-ethyl-3 ,5 '-dicarboxy-2- naphthamide is used in the fine grain green-sensitized emulsion instead of coupler 2-[a-(3-pentadecylphenoxy)butyramido]-5 -methoxyphenol. The photographic element is exposed as described in example 1 and processed as described in example 17 to produce in the photographic element good silver images and good diffusible dye images and to transfer imagewise the diffusible dye images to the mordant layer of the reception sheet.

in addition to the utility illustrated for my photographic elements in the preceding examples, they are used to advantage in other photographic recording systems where it is desired to record a plurality of separate images and be able to study them in superposed relationship especially when one or more of the images is made up of small and especially minute areas, such as, fine lines, small dots, etc. These very fine detailed images are vividly discernible when my photographic materials are used while they would be very diffieult to see when reproduced on prior art recording materials, especially in areas where there is an underlying image reproduction.

The invention has been described in detail with particular embodiments thereof, but it will be understood that variations and modifications can be effected within-the spirit and scope of the invention as described hereinabove and as defined in the appended claims lclaim:

l. A photographic element capable of recording images comprising a support having coated thereon l. a first light-sensitive hydrophilic colloid layer comprising a coarse grain silver halide emulsion. sensitive to at least one region of the actinic spectrum of from about Sm to about 1,200 my. which silver halide emulsions will record,

and a second light-sensitive hydrophilic colloid layer sensitive to at least one region of the said actinic spectrum that is different from the region of said actinic spectrum to which said silver halide emulsion in said first light-sensitive layer is sensitive, said second layer comprising a finer grained and more rapidly developing silver halide emulsion than the emulsion in said first lightsensitive layer, and contiguous to the silver halide grains of said emulsion in the said second light-sensitive layer, a nondiffusible coupler that reacts with oxidized primary aromatic amine color-developing agent to form a dye, and contiguous to silver halide grains in said second light-sensitive layer a nondiffusible development inhibitor-releasing hydroquinone compound that cross-oxidizes with oxidized primary aromatic amine color developer to release a diffusible development-inhibiting agent, said development inhibitor having substantially no development-inhibiting effect on the silver halide development in the second light-sensitive layer but produces a substantial inhibitionof the development of the said silver halide emulsion in the said first light-sensitive layer during color development of said element with a primary aromatic amine color developer; at least one of said first and said second light-sensitive layers containing a nondiffusible coupler which reacts with oxidized primary aromatic amine color-developing agent to form a dye and when both the said first and said second light-sensitive layers contain a nondiffusible coupler they are chosen so as to form upon reaction with oxidized color-developing agent two differently colored dyes.

A photographic camera speed element capable of recording images comprising a support having coated thereon:

l. a first light-sensitive hydrophilic colloid layer comprising a coarse grain silver halide emulsion sensitive to at least one region of the actinic spectrum of from about 5 mp to about 1,200 my and a nondiffusing coupler which reacts with an oxidized primary aromatic amine color-developing agent to form a nondiffusible dye, and

2. a second light-sensitive hydrophilic colloid layer sensitive to at least one region of the said actinic spectrum that is different from the region of said actinic spectrum to which said silver halide emulsion in said first light'sensi tive layer is sensitive, said second layer comprising a finer grained and more rapidly developing silver halide emulsion than the emulsion in said first light-sensitive layer, and contiguous to the silver halide grains of said emulsion in the said second light-sensitive layer, a nondiffusible coupler that reacts with oxidized primary aromatic amine color-developing agent to form a dye having a different color than the dye formed by the coupler in the said first light-sensitive layer, and contiguous to the said silver halide grains in said second light-sensitive layer a nondiffusi hle development inhibitor-releasing thioether hydroquinone compound that cross-oxidizes with an oxidized primary aromatic amine color developer to form a diffusible mercaptan development-inhibiting agent, said inhibitor having substantially no development-inhibiting effect on the silver halide development in the said second light-sensitive layer but produces a substantial inhibition of the development of the silver halide in the said first light-sensitive layer during color development of said element with a primary aromatic amine color developer.

3. A photographic element of claim 2 in which the nondiffusible development inhibitor-releasing thioether hydroquinone compound cross-oxidizes with an oxidized primary aromatic amine color-developing agent to form a diffusiblc heterocyclie mercapto development-inhibiting agent in which the heterocyclic ring has from four to six atoms in the ring with the heteroatoms being selected from the class consisting of nitrogen, oxygen, sullur and selenium such that the rmg has at least one nitrogen atom.

4. A photographic element of claim 2 in which the nondiffusible development inhibitor-releasing thioether hydroquin one compound cross-oxidizes with an oxidized primary aromatic amine color-developing agent to form a heterocyclic mercapto development-inhibiting agent in which the heterocyclic ring has from four to six atoms in the ring with the heteroatoms being selected from the class consisting of nitrogen, oxygen, sulfur and selenium such that the ring has at least one nitrogen atom and in which the said first light-sensitive hydrophilic colloid layer is coated as the first light-sensr tive layer on the said support and the said second light-sensitive hydrophilic colloid layer is coated over the said first lightsensitive hydrophilic colloid layer.

5. A photographic element of claim 2 in which the nondiffusible development inhibitor-releasing thioether hydroquinone compound cross-oxidizes with an oxidized primary aromatic amine color developing agent to form a diffusible heterocyclic mercapto development-inhibiting agent in which the heterocyclic ring has from four to six atoms in the ring with the heteroatoms being selected from the class consisting of nitrogen, oxygen, sulfur and selenium such that the ring has at least one nitrogen atom, and in which the said first light-sensitive layer and the said second light-sensitive layer are coated so that the said second light-sensitive layer is nearest the support and between the support and the said first light-sensitive layer.

6. A photographic element of claim 2 in which the support is a transparent support and in which the first light-sensitive hydrophilic colloid layer and the second light-sensitive hydrophilic colloid layers are separated by a hydrophilic colloid layer containing a bleachable blue light-absorber.

7. A photographic element of claim 2 in which the said first light-sensitive layer contains a blue-sensitive silver bromoiodide emulsion and the said second light-sensitive layer contains a green-sensitized silver chlorobromide emulsion.

8. A photographic element of claim 2 in which the said first light-sensitive layer contains a green-sensitized silver bromoiodide emulsion and the said second light-sensitive layer contains a blue-sensitive silver chlorobromide emulsion.

9. A photographic element of claim 2 in which the said first light-sensitive layer contains a blue-sensitive silver bromoiodide emulsion and the said second light-sensitive layer contains a red-sensitized silver chlorobromide emulsion.

10. A photographic element comprising a support coated in succession on one side with:

l. a first light-sensitive hydrophilic colloid layer comprising a camera speed fine grain rapidly developing silver chlorobromide emulsion sensitive to at least one region of the visible spectrum and contiguous to the said silver chlorobromide emulsion, a first colorless nondiffusible coupler that forms upon reaction with oxidized primary aromatic amine color-developing agent during color development a nondiffusible dye, and a nondiffusible development inhibitor-releasing thioether hydroquinone compound which cross-oxidizes with oxidized primary aromatic amine color-developing agent to release a diffusible development-inhibiting agent which has substantially no effect on the development of the said silver chlorobromide in l 2. a second light-sensitive hydrophilic colloid layer comprising a camera speed coarse grain silver bromoiodide emulsion sensitive to at least one region of the visible spectrum that is different than for said silver chlorobromide emulsion in l) and contiguous to silver bromoiodide grains in the said emulsion in (2). a colorless nondiffusible coupler selected from the class consisting of a S-pyrazolone, a phenol, a naphthol and an open chain coupler that forms upon reaction with oxidized primary aromatic amine, a nondiffusing dye having a color that is different from the color of the dye formed in the said first light-sensitive layer, the said coarse grain silver halide iodide emulsion having a developing induction period such that sufficient development inhibitor released by development in the said first light-sensitive layer diffuses into the said second light-sensitive layer before any latent image in the said silver bromoiodide emulsion starts to develop and substantially inhibits development of said latent image in areas corresponding to the nondiffusible dye formed in the said first light-sensitive layer, and a third light-sensitive hydrophilit colloid layer comprising a fine grain rapidly developing silver chlorobromide emulsion sensitive to at least one region of the visible spectrum that is different from the regions that the silver halide emplsions in (l and (2) are sensitive to and contiguous to silver chlorobromide grains in the emulsion in this layer, a third colorless nondiffusible coupler that forms upon reaction with oxidized primary aromatic amine color-developing agent during color development, a nondiffusible dye having a color that is different from the color of the dyes formed in the said first and said second light-sensitive layers, and a nondiffusible development inhibitor-releasing thioether hydroquinone compound which cross-oxidizes with oxidized primary aromatic amine color-developing agent to release a diffusible development-inhibiting agent which has substantially no effect on the development of the silver chlorobromide in the said third light-sensitive layer but which substantially inhibits development of any latent image in the said second light-sensitive layer in areas corresponding to the nondiffusible dye formed in the said third light-sensitive layer. 11. A photographic element comprising a support coated in succession with:

l. a first light-sensitive hydrophilic colloid layer comprising a coarse grain camera speed silver bromoiodide emulsion sensitive to one region of the visible spectrum and contiguous to the said silver bromoiodide emulsion, a colorless nondiffusible coupler selected from the class consisting of a S-pyrazolone, a phenol, a naphthol, and an openchain coupler that forms upon reaction with oxidized primary aromatic amine color-developing agent a nondiffusing dye and 2. a second light-sensitive hydrophilic colloid layer comprising a fine grain rapidly developing silver chlorobromide emulsion sensitive to at least one region of the visible spectrum that is different from the region to which the said silver bromoiodide emulsion is sensitive and contiguous to the said silver chlorobromide emulsion, a colorless nondiffusible coupler that forms upon color development a nondiffusible dye having a color that is different from the color of the dye formed in the said first light-sensitive layer and contiguous to said silver chlorobromide emulsion a nondiffusible thioether hydroquinone compound having the formula:

Q Q Qal wherein Q is selected from the group consisting of the hydrogen atom and an alkaline splittable acyl masking group; O is selected from the group consisting of the hydrogen atom and an alkaline splittable ACYL masking group; S is a monothio connecting radical; Rad is a heterocyclic radical which forms a mercaptan with said monothio connecting radical, said heterocyclic radical being selected from the class consisting of a 5- tetrazolyl group, a 2-benzoxazolyl group, a 2- benzothiazolyl group, a Z-oxadiazolyl group and a 2- thiadiazolyl group; Ball is a photographically inert organic ballasting radical of such molecular size and configuration as to render said hydroquinone compound nondiffusible; O is selected from the group consisting of the hydrogen atom, a SO M group and a COOM group; and M is an atom selected from the class consisting of hydrogen and an alkali metal.

12. A photographic element comprising a support coated in succession with:

1. a first light-sensitive gelatin layer comprising a green-sensitized coarse grain silver chlorobromoiodide emulsion and the nondiffusing magenta dye-forming coupler lphenyl-3- 3-[a-( 3-pentadecylphenoxy )acetamido] benzamido pyrazolone;

2. a gelatin layer containing 2-octadecyl-5sulfohydroquinone potassium salt; and

3. a second light-sensitive gelatin layer comprising a redsensitized fine grain rapidly developing gelatino silver chlorobromide emulsion, the nondiffusing cyan dyeforming coupler, l-hydroxy-N-[6-(2,4-di-t-amylphenoxy)butyl]-2-naphthamide and the development inhibitorreleasing hydroquinone compound 2-{4-[3-(4-t-amyl-xsulfophenoxy)-benzamido]phenethyl }-x-( l-phenyl-S- tetrazolylthio)hydroquinone diaeetate sodium salt dihydrate.

13. A photographic element comprising a support coated in succession with:

l. a first light-sensitive hydrophilic colloid layer comprising a blue-sensitive coarse grain camera speed gelatino silver bromoiodide emulsion and the two-equivalent magenta dye-forming coupler, l-(2,4,6-tirchlorophenyl)-3-pentadecyl-4-chloro-5 pyrazolone and 2. a second light-sensitive hydrophilic colloid layer compris ing a green-sensitized fine grain rapidly developing gelatino silver bromoiodide emulsion, the cyan dye-forming coupler, 2-[a-(3-pentadecylphenoxy)butyramido1-5- methoxyphenol and the development inhibitor-releasing hydroquinone, 2- I [3-[ 5-( B-carboxypropionamido )-2- (2,4-di-t-amylphenoxy)benzamido]ethyl}-3,5-dimethyl- 6-(2-oxadiazolylthio)hydroquinone.

14. A photographic element comprising a support coated in succession with:

l. a first light-sensitive hydrophilic colloid layer comprising a blue-sensitive coarse grain camera speed gelatino silver bromoiodide emulsion and the two-equivalent cyan dyeforming coupler, 2-[a-(2,4-di-t-amylphenoxy)butylamido]4,6-dichloro-5methylphenol,

2. a gelatin layer containing dioctyl hydroquinone and 3. a second light-sensitive hydrophilic colloid layer comprising a green-sensitized fine grain rapidly developing gelatino silver bromoiodide emulsion, the magenta dyeforming coupler, l-[4'('y -2,4-di-t-amylphenoxybutyramido)phenyl]3-ethoxy-5-pyrazolone, and the development inhibitor-releasing hydroquinone, 2-l4-[2- (2,4-di-t-amylphenoxy )-5-( 3,5-disulfamylbenzamido)benzamido]-phenethyl -3,5-dimethyl-6-( 5- methyl-2-thiadiazolylthio)hydroquinone.

15. A photographic element comprising a support coated in succession with:

l. a first light-sensitive hydrophilic colloid layer comprising a blue-sensitive coarse grain camera speed gelatino silver bromoiodide emulsion and the two-equivalent cyan dyeforming coupler, l-hydroxy-4-acetoxy-N-[a-(2,4-di-tamylphenoxy)butyl]2-naphthamide and 2. a second light-sensitive hydrophilic colloid layer comprising a green-sensitized fine grain rapid-developing gelatino silver bromoiodide emulsion and the magenta dye-forming coupler, lphenyl3pentadecyl-S-pyrazolone and the DIR hydroquinone compound, 5-[4-(3,5-disulfobenzamido)phenethyl]-2-methyl-3-( l-phenyl-S- tetrazolylthio)hydroquinone disodium salt.

16. A photographic element comprising a support having coated thereon:

l. a first light-sensitive hydrophilic colloid layer comprising a silver halide emulsion sensitive to at least one region of the actinic spectrum, and

2. a second light-sensitive hydrophilic colloid layer sensitive to at least one region of the actinic spectrum that is different from the region to which said first light-sensitive layer is sensitive, said second light-sensitive layer comprising a silver halide emulsion, and contiguous to the silver halide grains of said emulsion in the said second light-sensitive layer a nondiffusible development inhibitor-releasing hydroquinone compound having the formuwherein Q is selected from the group consisting of the hydrogen atom and an alkaline splittable acyl masking group; 0 is selected from the group consisting of the hydrogen atom and an alkaline splittable acyl masking group; S- is a monothio connecting radical; Rad is a photographically inert diffusible radical that forms a mercaptan with said monothio connecting radical; Ball is a photographically inert organic ballasting radical of such molecular size and configuration as to render said hydroquinone compound nondiffusible; and O is selected from the group consisting of the hydrogen atom, a SO M group and a COOM group; M is an atom selected from the class consisting of hydrogen and an alkali metal, said hydroquinone compound cross-oxidizes with oxidized primary aromatic amine color-developing agent to release the said mercaptan development inhibitor, that is capable of diffusing to said first light-sensitive layer to imagewise inhibit silver halide development therein, at least one of said first and said second light-sensitive layers containing a nondiffusible coupler which reacts with oxidized primary aromatic amine color-developing agent to form a nondiffusible dye and when both the said first and said second light-sensitive layers contain a nondiffusible coupler they are chosen so as to form upon reaction with oxidized colordeveloping agent two differently colored dyes.

17. A photographic element comprising the support having coated in succession on one side:

I. a red-sensitive gelatino silver bromoiodide emulsion layer containing the development inhibitor-releasing hydroquinone compound 2- l4-[ 3-(4-t-amyl-x-sulfophenoxy)benzamido1-phenethyl]-x-( l-phenyl-S- tetrazolylthio)hydroquinone sodium salt and the nondif fusing cyan dye-forming coupler l-hydroxy-N-[6-(2A-dit-amylphenoxy)butyl]-2-naphthamide; and

2. a green-sensitive gelatino silver bromoiodide emulsion layer containing the nondiffusing magenta dye-forming coupler l-( 2,4,6-trichlorophenyl)-3-{ 3-[ a-( 2,4-di-tamylphenoxy )acetamido1benzamido S-pyrazolone.

18. A process for color developing substantially all of a second latent image in a second light-sensitive silver halide emulsion layer of a photographic element and developing only those parts of a first latent image in a first light-sensitive silver halide emulsion layer of the said photographic element in which the said element comprises a support coated with: (a) the said first light-sensitive hydrophilic colloid layer containing a coarse grain silver halide emulsion and (b) the said second light-sensitive hydrophilic colloid layer comprising a fine grain rapidly developing silver halide emulsion and a non diffusing coupler that forms upon color development a nondiffusing dye in the said second light-sensitive layer and a nondiffusing development-releasing hydroquinone compound that cross-oxidizes with an oxidized primary aromuuc amine colordeveloping agent and releases a diffusible development inhibitor, said process comprising the step of contacting the said photographic element with an aqueous alkaline color \developer solution so that the latent image in the said second light-sensitive layer is rapidly converted into a silver and dye image and releases a corresponding imagewise pattern of development inhibitor. the said inhibitor having substantially no effect on image formation in the said second light-sensitive layer, and allowing the unused color developer solution containing the said imagewise pattern of development inhibitor to diffuse from the said second light-sensitive layer into and through the said first light-sensitive layer causing development of the said first latent image therein to a visible image only in areas outside the said imagewise pattern of development inhibitor and producing no visible image from any latent image in the said first light-sensitive layer between the said dye and silver image in the said second light-sensitive layer and the said support.

19. A process for recording two separate, differently colored light images as two different latent images, a first latent image in a first light-sensitive layer and a second latent image in a second light-sensitive layer in a photographic element and reproducing all of the said second latent image as a visible image and those parts of the said first latent image that are not superposed by the visible image reproduction of the said second latent image, the said process comprising the steps of:

l. exposing to the said two light images a photographic element comprising a support coated with: (a) a first lightsensitive hydrophilic colloid layer comprising a coarse grain camera speed silver bromoiodide emulsion responsive to only one of the said light images and a nondiffusing coupler that forms a nondiffusing dye upon color development, and (b) a second light-sensitive hydrophilic colloid layer comprising a fine grain rapidly developing silver chlorobromide emulsion responsive only to the other of said light images and contiguous to the said silver chlorobromide emulsion a nondiffusible coupler that forms upon color development a nondiffusible dye having a different color than the dye formed by color development of the coupler in the said first layer and contiguous to the said silver chlorobromide emulsion a nondiffusible development inhibitor-releasing hydroquinone compound that cross-oxidizes with oxidized primary aromatic amine color-developing agent to release a diffusible development-inhibiting agent which has substantially no development-inhibiting effect on the said silver chlorobromide emulsion but which inhibits development of the said silver bromoiodide emulsion in the said first light-sensitive layer during color development,

2. contacting the said photographic element with an aqueous alkaline solution containing a primary aromatic amine color-developing agent to develop a silver and dye image of the said second latent image in the second lightsensitive layer and to subsequently produce a differently colored dye image and a silver image of those areas of the said first latent image in the first light-sensitive layer which do not correspond to the said dye and silver image in the said second light-sensitive layer and producing substantially no visible image reproduction of any latent image in the first light-sensitive layer corresponding to the said dye and silver image in the said second light-sensitive layer.

20. A process for recording two separate, differently colored light images as two different latent images, a first latent image in a first light-sensitive layer and a second latent image in a second light-sensitive layer in a photographic element and reproducing all of the said second latent image as a visible image and those parts of the said first latent image that are not superposed by the visible image reproduction of the said second latent image, the said process comprising the steps l. exposing to the said two light images a photographic element comprising a support coated with: (a) a first lightsensitive hydrophilic colloid layer comprising a coarse grain camera speed silver bromoiodide emulsion responsive to only one of the said light images and a nondiffusing coupler that forms a diffusing dye upon color development, and (b) a second light-sensitive hydrophilic colloid layer comprising a fine grain rapidly developing silver chlorobromide emulsion responsive only to the other of said light images and contiguous to the said silver chlorobromide emulsion a nondiffusible coupler that forms upon color development a difi'usible dye having a different color than the dye formed by color development of the coupler in the said first layer and contiguous to the said silver chlorobromide emulsion a nondiffusible development inhibitor-releasing hydroquinone compound that cross-oxidizes with oxidized primary aromatic amine color-developing agent to release a diffusible development-inhibiting agent which has substantially no development-inhibiting effect on the said silver chlorobromide emulsion but which inhibits development of the said silver bromoiodide emulsion in the said first light-sensitive layer during color development,

2. contacting the outermost of said light-sensitive layers with the mordanted layer of a reception sheet in the presence of an aqueous alkaline solution containing a primary aromatic amine color-developing agent to develop a silver and a diffusible dye image of the said second latent image in the second light-sensitive layer and to develop a silver image and a differently colored diffusible dye image of those areas of the said first latent image in the first light-sensitive layer which do not correspond to the said dye and silver image in the said second light-sensitive layer and producing substantially no visible image reproduction ofany latent image in the first light-sensitive layer corresponding to the said dye and silver image in the said second light-sensitive layer, the said diffusible dye images transferring imagewise to the said mordantcd layer of said reception sheet, and

. separating the reception sheet with its composite dye image from the developed photographic element.

mg? UNITED STATES PATENT OFFICE CERTIFICATE 0F CORRECTION Patent No. 3 62TO71J6 Dated November 1971-" Inventor) Charles R. Barr It is certified that error appears in the above-identified patent and that said Letters Patent are hereby corrected as shown below:

"process" with -processes-. "Su" with --5mu; also "1 ,ZOO u" with --l ,200m 1-. "mu" with -my-.

line line line 56,

line 3 line 3 replace replace replace replace Column Column Column 5,

Column 8,

replace "benzoselenazoly(thio)" with line Column 9, line Column 10,line

57 "benzamidoih" with -benzamid o7-; "ditert.-" with di tert. "benzamidoih" with --benzamid 7-. replace entire line with -8-hyd roxy-loC- naphthoyll,2,3, l-

after 1" insert replace "tert-aylphenoxy)" with --tertamylphenoxy)-.

after "diethylaniline," delete "P" and insert -p;

line line 60, line 6?, Column 12 ,line 2 Column l3,line 7 line 8 Column 15 ,line 2 line 3 1, after "in" insert -its screen-; line 3U, after "and" delete "an" and insert --a-; line 59, replace "EXAMPLE" with --then--.

Column l6,line 15, after "a" insert -blue-sensitive-- Page one of two pages J after "pentadecyl-6" insert a hyphen "M050 UNITED STATES PATENT OFFICE (5 69) CERTIFICATE OF CORRECTION Patent No. 3 ,620 7 16 Dated ember 16, 1-971 Charles R. Barr Inventor(s) It is certified that error appears in the above-identified patent and that said Letters Patent are hereby corrected as shown below:

Column 16, line 16, replace "lchlorobromide" with -silver chlorobr'omide-; line 18, replace "an" with a; line 19 replace "an" with --a; line U2, after "5-" delete l7" and insert +=-L Column 17, line 11, replace "an" with -a--. Column 22, line 33, before "A" insert the number --2.-- Column 2 line 6 4, replace "ACYL" with --acyl-.

Signed and sealed this 6th day of June 1972.

(SEAL) Attest:

EDWARD M.FLETCHER,JR. ROBERT GO'ITSCHALK Attesting Officer Commissioner of Patents Page two of two pages 

2. a second light-sensitive hydrophilic colloid layer sensitive to at least one region of the said actinic spectrum that is different from the region of said actinic spectrum to which said silver halide emulsion in said first light-sensitive layer is sensitive, said second layer comprising a finer grained and more rapidly developing silver halide emulsion than the emulsion in said first light-sensitive layer, and contiguous to the silver halide grains of said emulsion in the said second light-sensitive layer, a nondiffusible coupler that reacts with oxidized primary aromatic amine color-developing agent to form a dye, and contiguous to silver halide grains in said second light-sensitive layer a nondiffusible development inhibitor-releasing hydroquinone compound that cross-oxidizes with oxidized primary aromatic amine color developer to release a diffusible development-inhibiting agent, said development inhibitor having substantially no development-inhibiting effect on the silver halide development in the second light-sensitive layer but produces a substantial inhibition of the development of the said silver halide emulsion in the said first light-sensitive layer during color development of said element with a primary aromatic amine color developer; at least one of said first and said second light-sensitive layers containing a nondiffusible coupler which reacts with oxidized primary aromatic amine color-developing agent to form a dye and when both the said first and said second light-sensitive layers contain a nondiffusible coupler they are chosen so as to form upon reaction with oxidized color-developing agent two differently colored dyes. A photographic camera speed element capable of recording images comprising a support having coated thereon:
 2. a second light-sensitive hydrophilic colloid layer sensitive to at least one region of the said actinic spectrum that is different from the region of said actinic spectrum to which said silver halide emulsion in said first light-sensitive layer is sensitive, said second layer comprising a finer grained and more rapidly developing silver halide emulsion than the emulsion in said first light-sensitive layer, and contiguous to the silver halide grains of said emulsion in the said second light-sensitive layer, a nondiffusible coupler that reacts with oxidized primary aromatic amine color-developing agent to form a dye having a different color than the dye formed by the coupler in the said first light-sensitive layer, and contiguous to the said silver halide grains in said second light-sensitive layer a nondiffusible development inhibitor-releasing thioether hydroquinone compound that cross-oxidizes with an oxidized primary aromatic amine color developer to form a diffusible mercaptan development-inhibiting agent, said inhibitor having substantially no development-inhibiting effect on the silver halide development in the said second light-sensitive layer but produces a substantial inhibition of the development of the silver halide in the said first light-sensitive layer during color development of said element with a primary aromatic amine color developer.
 2. a second light-sensitive hydrophilic colloid layer comprising a camera speed coarse grain silver bromoiodide emulsion sensitive to at least one region of the visible spectrum that is different than for said silver chlorobromide emulsion in (1) and contiguous to silver bromoiodide grains in the said emulsion in (2), a colorless nondiffusible coupler selected from the class consisting of a 5-pyrazolone, a phenol, a naphthol and an open chain coupler that forms upon reaction with oxidized primary aromatic amine, a nondiffusing dye having a color that is different from the color of the dye formed in the said first light-sensitive layer, the said coarse grain silver halide iodide emulsion having a developing induction period such that sufficient development inhibitor released by development in the said first light-sensitive layer diffuses into the said second light-sensitive layer before any latent image in the said silver bromoiodide emulsion starts to develop and substantially inhibits development of said latent image in areas corresponding to the nondiffusible dye formed in the said first light-sensitive layer, and
 2. a second light-sensitive hydrophilic colloid layer comprising a fine grain rapidly developing silver chlorobromIde emulsion sensitive to at least one region of the visible spectrum that is different from the region to which the said silver bromoiodide emulsion is sensitive and contiguous to the said silver chlorobromide emulsion, a colorless nondiffusible coupler that forms upon color development a nondiffusible dye having a color that is different from the color of the dye formed in the said first light-sensitive layer and contiguous to said silver chlorobromide emulsion a nondiffusible thioether hydroquinone compound having the formula:
 2. a gelatin layer containing 2-octadecyl-5-sulfohydroquinone potassium salt; and
 2. a second light-sensitive hydrophilic colloid layer comprising a green-sensitized fine grain rapidly developing gelatino silver bromoiodide emulsion, the cyan dye-forming coupler, 2-( Alpha -(3-pentadecylphenoxy)butyramido)-5-methoxyphenol and the development inhibitor-releasing hydroquinone, 2- Beta -(5-( Beta -carboxypropionamido)-2-(2,4-di-t-amylphenoxy)benzamido) ethyl -3,5-dimethyl-6-(2-oxadiazolylthio)hydroquinone.
 2. a gelatin layer containing dioctyl hydroquinone and
 2. a second light-sensitive hydrophilic colloid layer comprising a green-sensitized fine grain rapid-developing gelatino silver bromoiodide emulsion and the magenta dye-forming coupler, 1-phenyl-3-pentadecyl-5-pyrazolone and the DIR hydroquinone compound, 5-(4-(3,5-disulfobenzamido)phenethyl)-2-methyl-3-(1-phenyl-5 -tetrazolylthio)hydroquinone disodium salt.
 2. a second light-sensitive hydrophilic colloid layer sensitive to at least one region of the actinic spectrum that is different from the region to which said first light-sensitive layer is sensitive, said second light-sensitive layer comprising a silver halide emulsion, and contiguous to the silver halide grains of said emulsion in the said second light-sensitive layer a nondiffusible development inhibitor-releasing hydroquinone compound having the formula:
 2. a green-sensitive gelatino silver bromoiodide emulsion layer containing the nondiffusing magenta dye-forming coupler 1-(2,4, 6-trichloRophenyl)-3- 3-( Alpha -(2,4-di-t-amylphenoxy)acetamido)benzamido -5-pyrazolone.
 2. contacting the said photographic element with an aqueous alkaline solution containing a primary aromatic amine color-developing agent to develop a silver and dye image of the said second latent image in the second light-sensitive layeR and to subsequently produce a differently colored dye image and a silver image of those areas of the said first latent image in the first light-sensitive layer which do not correspond to the said dye and silver image in the said second light-sensitive layer and producing substantially no visible image reproduction of any latent image in the first light-sensitive layer corresponding to the said dye and silver image in the said second light-sensitive layer.
 2. contacting the outermost of said light-sensitive layers with the mordanted layer of a reception sheet in the presence of an aqueous alkaline solution containing a primary aromatic amine color-developing agent to develop a silver and a diffusible dye image of the said second latent image in the second light-sensitive layer and to develop a silver image and a differently colored diffusible dye image of those areas of the said first latent image in the first light-sensitive layer which do not correspond to the said dye and silver image in the said second light-sensitive layer and producing substantially no visible image reproduction of any latent image in the first light-sensitive layer corresponding to the said dye and silver image in the said second light-sensitive layer, the said diffusible dye images transferring imagewise to the said mordanted layer of said reception sheet, and
 3. separating the reception sheet with its composite dye image from the developed photographic element.
 3. separating the reception sheet with its composite dye image from the developed photographic element.
 3. a second light-sensitive hydrophilic colloid layer comprising a green-sensitized fine grain rapidly developing gelatino silver bromoiodide emulsion, the magenta dye-forming coupler, 1-(4-( gamma -2,4-di-t-amylphenoxybutyramido)phenyl) -3-ethoxy-5-pyrazolone, and the development inhibitor-releasing hydroquinone, 2- 4-(2-(2,4-di-t-amylphenoxy)-5-(3,5-disulfamylbenzamido)benzamido)-phenethyl -3,5-dimethyl-6-(5-methyl-2-thiadiazolylthio)hydroquinone.
 3. a second light-sensitive gelatin layer comprising a red-sensitized fine grain rapidly developing gelatino silver chlorobromide emulsion, the nondiffusing cyan dye-forming coupler, 1-hydroxy-N-( delta -(2,4-di-t-amylphenoxy)butyl)-2-naphthamide and the development inhibitor-releasing hydroquinone compound 2- 4-(3-(4-t-amyl-x-sulfophenoxy)-benzamido)phenethyl -x-(1-phenyl-5-tetrazolylthio)hydroquinone diacetate sodium salt dihydrate.
 3. a third light-sensitive hydrophilic colloid layer comprising a fine grain rapidly developing silver chlorobromide emulsion sensitive to at least one region of the visible spectrum that is different from the regions that the silver halide emulsions in (1) and (2) are sensitive to and contiguous to silver chlorobromide grains in the emulsion in this layer, a third colorless nondiffusible coupler that forms upon reaction with oxidized primary aromatic amine color-developing agent during color development, a nondiffusible dye having a color that is different from the color of the dyes formed in the said first and said second light-sensitive layers, and a nondiffusible development inhibitor-releasing thioether hydroquinone compound which cross-oxidizes with oxidized primary aromatic amine color-developing agent to release a diffusible development-inhibiting agent which has substantially no effect on the development of the silver chlorobromide in the said third light-sensitive layer but which substantially inhibits development of any latent image in the said second light-sensitive layer in areas corresponding to the nondiffusible dye formed in the said third light-sensitive layer.
 3. A photographic element of claim 2 in which the nondiffusible development inhibitor-releasing thioether hydroquinone compound cross-oxidizes with an oxidized primary aromatic amine color-developing agent to form a diffusible heterocyclic mercapto development-inhibiting agent in which the heterocyclic ring has from four to six atoms in the ring with the heteroatoms being selected from the class consisting of nitrogen, oxygen, sulfur and selenium such that the ring has at least one nitrogen atom.
 4. A photographic element of claim 2 in which the nondiffusible development inhibitor-releasing thioether hydroquinone compound cross-oxidizes with an oxidized primary aromatic amine color-developing agent to form a heterocyclic mercapto development-inhibiting agent in which the heterocyclic ring has from four to six atoms in the ring with the heteroatoms being selected from the class consisting of nitrogen, oxygen, sulfur and selenium such that the ring has at least one nitrogen atom and in which the said first light-sensitive hydrophilic colloid layer is coated as the first light-sensitive layer on the said support and the said second light-sensitive hydrophilic colloid layer is coated over the said first light-sensitive hydrophilic colloid layer.
 5. A photographic element of claim 2 in which the nondiffusible development inhibitor-releasing thioether hydroquinone compound cross-oxidizes with an oxidized primary aromatic amine color developing agent to form a diffusible heterocyclic mercapto development-inhibiting agent in which the heterocyclic ring has from four to six atoms in the ring with the heteroatoms being selected from the class consisting of nitrogen, oxygen, sulfur and selenium such that the ring has at least one nitrogen atom, and in which the said first light-sensitive layer and the said second light-sensitive layer are coated so that the said second light-sensitive layer is nearest the support and between the support and the said first light-sensitive layer.
 6. A photographic element of claim 2 in which the support is a transparent support and in which the first light-sensitive hydrophilic colloid layer and the second light-sensitive hydrophilic colloid layers are separated by a hydrophilic colloid layer containing a bleachable blue light-absorber.
 7. A photographic element of claim 2 in which the said first light-sensitive layer contains a blue-sensitive silver bromoiodide emulsion and the said second light-sensitive layer contains a green-sensitized silver chlorobromide emulsion.
 8. A photographic element of claim 2 in which the said first light-sensitive layer contains a green-sensitized silver bromoiodide emulsion and the said second light-sensitive layer contains a blue-sensitive silver chlorobromide emulsion.
 9. A photographic element of claim 2 in which the said first light-sensitive layer contains a blue-sensitive Silver bromoiodide emulsion and the said second light-sensitive layer contains a red-sensitized silver chlorobromide emulsion.
 10. A photographic element comprising a support coated in succession on one side with:
 11. A photographic element comprising a support coated in succession with:
 12. A photographic element comprising a support coated in succession with:
 13. A photographic element comprising a support coated in succession with:
 14. A photographic element comprising a support coated in succession with:
 15. A photographic element comprising a support coated in succession with:
 16. A photographic element comprising a support having coated thereon:
 17. A photographic element comprising the support having coated in succession on one side:
 18. A process for color developing substantially all of a second latent image in a second light-sensitive silver halide emulsion layer of a photographic element and developing only those parts of a first latent image in a first light-sensitive silver halide emulsion layer of the said photographic element in which the said element comprises a support coated with: (a) the said first light-sensitive hydrophilic colloid layer containing a coarse grain silver halide emulsion and (b) the said second light-sensitive hydrophilic colloid layer comprising a fine grain rapidly developing silver halide emulsion and a nondiffusing coupler that forms upon color development a nondiffusing dye in the said second light-sensitive layer and a nondiffusing development-releasing hydroquinone compound that cross-oxidizes with an oxidized primary aromatic amine color-developing agent and releases a diffusible development inhibitor, said process comprising the step of contacting the said photographic element with an aqueous alkaline color developer solution so that the latent image in the said second light-sensitive layer is rapidly converted into a silver and dye image and releases a corresponding imagewise pattern of development inhibitor, the said inhibitor having substantially no effect on image formation in the said second light-sensitive layer, and allowing the unused color developer solution containing the said imagewise pattern of development inhibitor to diffuse from the said second light-sensitive layer into and through the said first light-sensitive layer causing development of the said first latent image therein to a visible image only in areas outside the said imagewise pattern of development inhibitor and producing no visible image from any latent image in the said first light-sensitive layer between the said dye and silver image in the said second light-sensitive layer and the said support.
 19. A process for recording two separate, differently colored light images as two different latent images, a first latent image in a first light-sensitive layer and a second latent image in a second light-sensitive layer in a photographic element and reproducing all of the said second latent image as a visible image and those parts of the said first latent image that are not superposed by the visible image reproduction of the said second latent image, the said process comprising the steps of:
 20. A process for recording two separate, differently colored light images as two different latent images, a first latent image in a first light-sensitive layer and a second latent image in a second light-sensitive layer in a photographic element and reproducing all of the said second latent image as a visible image and those parts of the said first latent image that are not superposed by the visible image reproduction of the said second latent image, the said process comprising the steps of: 